Polyalkenyl ether resin

ABSTRACT

There are provided a polyalkenyl ether type polyurethane, which is excellent in flexibility, aor the like, and which has in the molecule, a structural unit represented by formula (XXX):  
                 
 
(wherein n represents an integer of 2 to 1000, R 1  represents substituted or unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted aralkyl, and R 2 , R 3  and R 4 , which are the same or different, each represent a hydrogen atom, substituted or unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl or substituted or unsubstituted aralkyl, and R 1 s, R 2 s, R 3 s, and R 4 s, when they are each present two or more in number, may be respectively the same or different), and the like.

TECHNICAL FIELD

The present invention relates to a polyurethane, a polyester, and thelike useful for applications such as paints, coating agents, inks,adhesives, films, fibers, photoresists, solder resists, semiconductorsealing materials, laminated sheets, shaping materials, sealing agents,molding materials, or the like, or the raw materials therefor.

BACKGROUND ART

A polyurethane, a polyester, an epoxy resin, and light/electron beamcurable resins thereof have been widely used in applications such aspaints, coating agents, inks, adhesives, photoresists, sealing agents,binders, and molding materials.

The above-mentioned resins having polyether skeletons, polydieneskeletons, or the like known in the art are not satisfactory in terms offlexibility, compatibility with low polarity resins, uniformity ofcomposition, mechanical strength, solubility, stickiness, bondingproperty, adhesion, electrical insulation property, weather resistance,water resistance, transparency, results in a pressure cooker test whichare the required characteristics of a substrate for an electroniccircuit, and the like.

Macromolecular Chemistry and Physics, 198, 3051-3064 (1997) discloses apolyurethane having a poly(2-chloroethyl vinyl ether) skeleton. A resinhaving a poly(2-chloroethyl vinyl ether) skeleton has problems instability, for example, that it causes a dechlorination reaction underheating conditions. Further, a 2-chloroethyl vinyl ether, which is theraw material therefor, has become a regulated substance in the WasteDisposal Law and the Living Environment Conservation Ordinance, andaccordingly it is considered that the environment is adversely affectedthereby.

DISCLOSURE OF THE PRESENT INVENTION

An object of the present invention is to provide a polyurethane, apolyester, and the like, which are excellent in flexibility,compatibility with a low polarity resin, uniformity of composition,mechanical strength, solubility, stickiness, bonding property, adhesion,electrical insulation property, weather resistance, water resistance,transparency, thermal aging resistance, results in a pressure cookertest, or the like.

The present invention provides the following (1) to (24):

-   (1) A polyurethane having, in the molecule, a structural unit    represented by formula (XXX):    (wherein n represents an integer of 2 to 1000, R¹ represents a    substituted or unsubstituted lower alkyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted aryl, or    substituted or unsubstituted aralkyl, and R², R³ and R⁴, which are    the same or different, each represent a hydrogen atom, substituted    or unsubstituted lower alkyl, substituted or unsubstituted    cycloalkyl, substituted or unsubstituted aryl, or substituted or    unsubstituted aralkyl, and R¹s, R²s, R³s, and R⁴s, when they are    each present two or more in number, may be respectively the same or    different). Hereinafter, the polyurethane also be reffered to as    Polyurethane (I).-   (2) A polyurethane having, in the molecule, a structural unit    represented by formula (I):    (wherein n, R¹, R², R³ and R⁴ respectively have the same meanings as    defined above, R⁵ represents a hydrogen atom, substituted or    unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted aryl, or substituted or unsubstituted    aralkyl).-   (3) The polyurethane according to the above (1) or (2), wherein the    weight-average molecular weight therof is 30000 to 1000000.-   (4) An urethane acrylate having, in the molecule the structural unit    represented by formula (XXX) described in the above (1).    Hereinafter, the urethane acrylate also be referred to as Urethane    acrylate (II).-   (5) An urethane acrylate having, in the molecule a structural unit    represented by formula (II):    (wherein n, R¹, R², R³, R⁴, and R⁵ respectively have the same    meanings as defined above, R⁹ represents a residue derived from a    polyisocyanate compound, R¹⁰ represent substituted or unsubstituted    lower alkylene, substituted or unsubstituted. cycloalkylene or    substituted or unsubstituted arylene, and R¹¹, R¹² and R¹³, which    are the same or different, each represent a hydrogen atom,    substituted or unsubstituted lower alkyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted aryl, or    substituted or unsubstituted aralkyl).-   (6) The urethane acrylate according to the above (4) or (5), wherein    the number-average molecular weight thereof is 200 to 10000.-   (7) A composition comprising the urethane acrylate according to any    of the above (4) to (6) and a radical photo-, or thermal    polymerization initiator.-   (8) An urethane alkenyl ether having, in the molecule, the    structural unit represented by formula (XXX) described in the above    (1). Hereinafter, the urethane alkenyl ether also be reffered to as    Urethane alkenyl ether (XI).-   (9) An urethane alkenyl ether having, in the molecule, a structural    unit represented by formula (XI):    (wherein n, R¹, R², R³, R⁴ and R⁵respectively have the same meanings    as defined above, R³³ represents a residue derived from a    polyisocyanate compound, R³⁴ represents substituted or unsubstituted    lower alkylene, substituted or unsubstituted cycloalkylene, or    substituted or unsubstituted arylene, and R³⁵, R³⁶ and R³⁷, which    are the same or different, each represent a hydrogen atom,    substituted or unsubstituted lower alkyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted aryl or    substituted or unsubstituted aralkyl).-   (10) The urethane alkenyl ether according to the above (8) or (9),    wherein the number-average molecular weight thereof is 200 to 10000.-   (11) A composition comprising the urethane alkenyl ether according    to any of the above (8) to (10), and a polymerization initiator    generating an acid through heating or light irradiation.-   (12) A composition comprising the urethane alkenyl ether according    to any of the above (8) to (10), and a compound having a maleimido    group.-   (13) A polyester derived from a polyol, said polyol having, in the    molecule, a structural unit represented by formula (XXX) described    in the above (1) and having hydroxyl groups at 2, 3 or 4 ends.    Hereinafter, the polyester also be referred to as Polyester (III).-   (14) A polyester having, in the molecule, a structural unit    represented by formula (III):    (wherein n, R¹, R², R³, R⁴ and R⁵ respectively have the same    meanings as defined above, and R¹⁴ represents substituted or    unsubstituted lower alkylene, substituted or unsubstituted    cycloalkylene, or substituted or unsubstituted arylene).-   (15) The polyester according to the above (13) or (14), wherein the    weight-average molecular weight thereof is 30000 to 1000000.-   (16) An ester acrylate derived from a polyol, said polyol having, in    the molecule, a structural unit represented by formula (XXX)    described in the above (1) and having hydroxyl groups at 2, 3 or 4    ends. Hereinafter, the ester acrylate also be,referred to as Ester    acrylate (IV).-   (17) An ester acrylate having, in the molecule, a structural unit    represented by formula (IV):    (wherein n, R¹, R², R³, R⁴ and R⁵respectively have the same meanings    as defined above, and R¹⁵, R¹⁶ and R¹⁷, which are the same or    different, each represent a hydrogen atom, substituted or    unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted aryl, or substituted or unsubstituted    aralkyl).-   (18) The ester acrylate according to the above (16) or (17), wherein    the number-average molecular weight thereof is 200 to 10000.-   (19) A composition comprising the ester acrylate according to any of    the above (16) to (18), and a radical photo-, or thermal    polymerization initiator.-   (20) An alkenyl ether having, in the molecule, the structural unit    represented by formula (XXX) described in the above (1).    Hereinafter, the alkenyl ether also be referred to as Alkenyl ether    (V).-   (21) An alkenyl ether having, in the molecule, a structural unit    represented by formula (V):    (wherein n, R¹, R², R³, R⁴, and R⁵ respectively have the same    meanings as defined above, R¹⁸, R¹⁹ and R²⁰, which are the same or    different, each represent a hydrogen atom, substituted or    unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted aryl, or substituted or unsubstituted    aralykyl).-   (22) The alkenyl ether according to the above (20) or (21), wherein    the number-average molecular weight thereof is 200 to 10000.-   (23) A composition comprising the alkenyl ether according to any of    the above (20) to (22) and a polymerization initiator generating an    acid through heating or light irradiation.-   (24) A composition comprising the alkenyl ether according to any of    the above (20) to (22) and a compound having a maleimido group.

The present invention will be described below in detail.

In the definition of groups in the above formulae, the lower alkylincludes a straight-chain or branched alkyl groups having 1 to 8 carbonatoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,tert-butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, andoctyl. As the lower alkylene, mentioned are the one obtained by removingone hydrogen atom from the above mentioned lower alkyl, and the like.

The cycloalkyl includes cycloalkyl groups having 3 to 10 carbon atomssuch as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, and cyclodecyl. As the cycloalkylene, mentionedare the one obtained by removing one hydrogen atom from theabove-mentioned cycloalkyl, and the like.

The aryl and the aryl moiety of the aralkyl include aryls having 6 to 14carbon atoms such as phenyl, naphthyl and anthryl. As the alkylenemoiety of the aralkyl, mentioned are the one obtained by removing one ortwo hydrogen atoms from the above-mentioned lower alkyl, and the like.Specific examples of the aralkyl include benzyl, phenethyl,phenylpropyl, naphthylmethyl, naphthylethyl, and diphenylmethyl. As thearylene, mentioned are the one obtained by removing one hydrogen atomfrom the above mentioned aryl, and the like.

As the polyisocyanate compound in the residue derived from apolyisocyanate compound, examples include aromatic polyisocyanates suchas diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylenediisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate,2,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, andp-xylylene diisocyanate, alicyclic polyisocyanates such as isophoronediisocyanate, 4,4′-diisocyanate dicyclohexane, and 4,4′-diisocyanatedicyclohexylmethane, and aliphatic polyisocyanates such as hexamethylenediisocyanate, tetramethylene diisocyanate, lysine ester diisocyanate,and lysine ester triisocyanate.

As the residue derived from a polyisocyanate compound, preferred issubstituted or unsubstituted lower alkylene, substituted orunsubstituted cycloalkylene, or substituted or unsubstituted arylene. Asthe lower alkylene, the cycloalkylene, and the arylene, mention be madeof the same ones as described above, respectively. As the substituentsin the substituted lower alkylene, the substituted cycloalkylene, andthe substituted arylene, mention be made of the same ones as thoseexemplified in the definition of the substituent in the substitutedlower alkyl described later.

As the substitutents in the substituted lower alkyl, the substitutedcycloalkyl, the substituted aryl, the substituted aralkyl, thesubstituted lower alkylene, the substituted cycloalkylene, and thesubstituted arylene, examples include hydroxy, lower alkyl, loweralkoxy, lower alkoxycarbonyl, lower alkanoyl, cinnamoyloxy, aroyloxy,and a halogen atom. Although the number of substituents is notparticularly limited, it is preferably 1 to 3.

In the definition of the substituents, the alkyl moieties of the loweralkyl, the lower alkoxy, the lower alkoxycarbonyl, and the loweralkanoyl, have the same meanings as the definition of the lower alkyldescribed above. As the aryl moiety of the aroyloxy, mention be made ofthe same ones as those exemplified in the definition of the aryldescribed above. As the halogen atom, mention be made of respectiveatoms of fluorine, chlorine, bromine, iodine, and astatine.

Among the polyurethanes having a structural unit represented by formula(I) in the molecule, the urethane acrylates having a structural unitrepresented by formula (II) in the molecule, the urethane alkenyl ethershaving a structural unit represented by formula (XI) in the molecule,the polyesters having a structural unit represented by formula (III) inthe molecule, the ester acrylates having a structural unit representedby formula (IV) in the molecule, and the alkenyl ethers having astructural unit represented by formula (V) in the molecule, compoundswhere R¹ is lower alkyl, and R², R³, R⁴ and R⁵ are each a hydrogen atomare preferable, respectively.

(1) Raw Material Compound

A raw material for the polyurethane or the like of the presentinvention, preferred to a polyol having the structural unit representedby formula (XXX) in the molecule, and having hydroxyl groups(hereinafter, the polyol also be referred to as Compound A). Morepreferred to examples thereof include the compound represented by theformula (A):

[wherein n, R¹, R² R³, R⁴ and R⁵ have the same meanings as definedabove, m represents an integer of 1 to 4, X represents a hydrogen atom,a substituted or unsubstituted lower alkylene, -Q¹-A-Q²- (wherein Arepresents a substituted or unsubstituted cycloalkylene or a substitutedor unsubstituted arylene, and Q¹ and Q², which are the same ordifferent, and each denote a single bond or a substituted orunsubstituted lower alkylene), a substituted or unsubstituted loweralkanetriyl, formula (B)

(wherein A¹ represents a substituted or unsubstituted cycloalkanetriylor a substituted or unsubstituted aromatic ring triyl, Q³, Q⁴ and Q⁵,which are the same or different, each represents a single bond or asubstituted or unsubstituted lower alkylene), or formula (C)

(wherein A² represents a carbon atom, a substituted or unsubstitutedalicyclic hydrocarbon tetrayl or a substituted or unsubstituted aromatichydrocarbon tetrayl, and Q⁶, Q⁷, Q⁸ and Q⁹, which are the same ordifferent, each represents a single bond or a substituted orunsubstituted lower alkylene), and when m is 2 or more, respective n'sbe the same or different].

These raw materials can be obtained in the following manner. Forexample, the corresponding alkenyl ether monomer, and if required, acation polymerizable monomer which is copolymerizable therewith aresubjected to homopolymerization or copolymerization in the presence of amultifunctional initiator and Lewis acid with a known method [e.g.,Mitsuo Sawamoto, SHINNKOUBUNNSHI JIKKENNGAKU 2 KOUBUNNSHI NOGOUSEI/HANNOU (1), p.p., 242-276, edited by the Society of PolymerScience, Japan, KYOURITSU SHUPPAN (1995)], to obtain a polyalkenyl ether(copolymer) having acetals at 2, 3 or 4 ends. The obtained copolymer issubjected to acid hydrolyzation to obtain be a polyalkenyl ether(copolymer) having formyl groups at 2, 3 or 4 ends. Finally, theresulting copolymer is subjected to a reduction treatment.

Specific examples of the alkenyl ether monomer include methyl vinylether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,isobutyl vinyl ether, 2-vinyloxyethyl benzoate, 2-acetoxyethyl vinylether, 2-ethoxyethyl vinyl ether, diethyl[2-(vinyloxy)ethyl]malonate,3-tris(ethoxycarbonyl)propyl vinyl ether, 2-vinyloxyethyl cinnamate,cyclohexyl vinyl ether, 4-fluorobutyl vinyl ether, 3-bromobutyl vinylether, 4-ethoxybutyl vinyl ether, methylpropenyl ether, ethylpropenylether, isopropyl propenyl ether, n-butyl propenyl ether, isobutylpropenyl ether, cyclohexyl propenyl ether, n-propyl vinyl ether,4-methyl-2-pentyl vinyl ether, n-hexyl vinyl ether, n-heptyl vinylether, 3-methyl-1-hexyl vinyl ether, 5-methyl-1-hexyl vinyl ether, and2-ethyl-1-hexyl vinyl ether. These are used alone, or in mixture of twoor more thereof.

The cation polymerizable monomer which is copolymerizable with analkenyl ether monomer has no particular restriction. Specific preferredto examples thereof include styrene, α-methylstyrene, isobutene, N-vinylcarbazole, p-methoxystyrene, n-nonyl vinyl ether, isononyl vinyl ether,n-decyl vinyl ether, isodecyl vinyl ether, n-undecyl vinyl ether,isoundecyl vinyl ether, n-dodecyl vinyl ether, isododecyl vinyl ether,n-tridecyl vinyl ether, isotridecyl vinyl ether, n-tetradecyl vinylether, isotetradecyl vinyl ether, n-pentadecyl vinyl ether,isopentadecyl vinyl ether, n-hexadecyl vinyl ether, isohexadecyl vinylether, n-heptadecyl vinyl ether, isoheptadecyl vinyl ether, n-octadecylvinyl ether, isooctadecyl vinyl ether, n-nonadecyl vinyl ether,isononadecyl vinyl ether, n-eicosyl vinyl ether, isoeicosyl vinyl ether,and n-hexadecyl propenyl ether. The amount of the copolymerizablemonomers to be used is preferably 50 wt % or less based on the totalamount of monomers to be used for polymerization.

As the multifunctional initiator usable are a compound represented byformula (X):

(wherein R²⁹ represents a hydrogen atom, a substituted or unsubstitutedlower alkyl, a substituted or unsubstituted cycloalkyl, a substituted orunsubstituted aryl, or a substituted or unsubstituted aralkyl, R³⁰, R³¹and R³², which are the same or different, each represents a substitutedor unsubstituted lower alkyl, a substituted or unsubstituted cycloalkyl,a substituted or unsubstituted aryl, or a substituted or unsubstitutedaralkyl), and a compound represented by formula (IX)

[wherein R⁹⁹ represents a substituted or unsubstituted lower alkylene,-Q¹-A-Q²- (wherein A, Q¹ and Q² respectively have the same meanings asdefined above), a substituted or unsubstituted lower alkanetriyl,formula (B):

(wherein A¹, Q³, Q⁴, and Q⁵ respectively have the same meanings asdefined above), or formula (C):

(where in the formula, A², Q⁶, Q⁷, Q⁸, and Q⁹ are respectively have thesame meanings as defined above), R¹⁰⁰ represents a hydrogen atom, asubstituted or unsubstituted lower alkyl, a substituted or unsubstitutedcycloalkyl, a substituted or unsubstituted aryl, or a substituted orunsubstituted aralkyl, p represents an integer of 2 to 4, and Zrepresents a lower alkanoyloxy, a lower alkoxy, hydroxy, or a halogenatom].

In the definition of each group in formula (A), -Q¹-A-Q²-, formula (B),formula (C), formula (X), and formula (IX), a substituted orunsubstituted lower alkyl, a substituted or unsubstituted cycloalkyl, asubstituted or unsubstituted aryl, a substituted or unsubstitutedaralkyl, a substituted or unsubstituted lower alkylene, a substituted orunsubstituted cycloalkylene, and a substituted or unsubstituted arylenerespectively have the same meanings as defined above. The substituted orunsubstituted lower alkanetriyl include those obtained by removing twohydrogen atoms from the substituted or unsubstituted lower alkyl, or thelike. The substituted or unsubstituted cycloalkanetriyl include thoseobtained by removing two hydrogen atoms from the substituted orunsubstituted cycloalkyl, or the like. As the aromatic ring moiety of asubstituted or unsubstituted aromatic ring triyl, mentioned an aromaticring having 6 to 14 carbon atoms. Specific examples thereof includebenzene, naphthalene and anthracene. The substituted or unsubstitutedalicyclic hydrocarbon tetrayl includes those obtained by removing 3hydrogen atoms from the substituted or unsubstituted cycloalkyl, or thelike. The substituted or unsubstituted aromatic hydrocarbon tetraylinclude obtained by removing 3 hydrogen atoms from the substituted orunsubstituted aryl, or the like.

Examples of the substituents in a substituted aromatic ring triyl, asubstituted alicyclic hydrocarbon tetrayl, and a substituted aromatichydrocarbon tetrayl include hydroxy, lower alkyl, lower alkoxy, loweralkoxycarbonyl, lower alkanoyl, cinnamoyloxy, aroyloxy, and halogenatom. Although the number of substituents has no particular restriction,it is preferably 1 to 3.

In the definition of each substituent, as the alkyl moieties of loweralkyl, lower alkoxy, lower alkoxycarbonyl, and lower alkanoyl, mentionbe made of the same ones as those exemplified in the definition of thelower alkyl. As the aryl moieties of aroyloxy, mention be made of thesame ones as those exemplified in the definition of the aryl. As thehalogen atoms, mention be made of the same ones as those mentionedabove.

More specific examples of the multifunctional initiator include organicacid, inorganic acid, and alcohol adducts of multifunctional alkenylethers.

Examples of the multifunctional alkenyl ether include ethylene glycoldivinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinylether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether,diethylene glycol divinyl ether, glycerin trivinyl ether,trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether,bisphenol F divinyl ether, bisphenol A divinyl ether, 1,3,5-tris(2-hydroxyethyl) cyanurate trivinyl ether, and vinyl ethers of phenolresins or novolak resins. As an organic acid to be added to amultifunctional alkenyl ether include formic acid, acetic acid,propionic acid, and butanoic acid; As an inorganic acid to be added to amultifunctional alkenyl ether, examples include hydrochloric acid,hydrobromic acid, and hydroiodic acid; and as the alcohol to be added toa multifunctional alkenyl ether,examples include methanol, ethanol, and(iso)propyl alcohol.

Lewis acids have no particular restriction, and preferred are metalhalides or complexes thereof (such as diethyl ether complexes, aceticacid complexes, water complexes, and methanol complexes), and examplesinclude BCl₃, BF₃, BF₃.O(CH₂CH₃)₂, TiCl₄, SnCl₄, SnBr₄, AlCl₃, SbCl₅,SbF₅, WCl₆, and TaCl₅, or complexes thereof. Among the examples,preferred are halides of tin, boron, or aluminum (such as BF₃, SnCl₄,and AlCl₃) or complexes thereof are preferred, and more preferred areBF₃(boron trifluoride) or complexes thereof. As the Lewis acid, used isthe metal halaide in which the halogen atom is substituted with loweralkyl, lower alkoxy, phenoxy, or the like. Herein, the lower alkyl andthe lower alkoxy respectively have the same meanings as defined above.The amount of Lewis acid to be used has no particular restriction, andis preferably 0.00001 to 3.0 mol per mole of the alkenyl ether monomer.

For the polymerization reaction, if required, the Lewis base be added.Examples of Lewis base include ethyl acetate, ethyl chloroacetate,diethyl carbonate, dioxane, tetrahydrofuran, diethyl ether,tetrahydrothiophene and 2,6-dimethylpyridine. The amount of the Lewisbase to be used has no particular restriction, and is preferably 0.001to 100 mol per mole of the alkenyl ether monomer.

The polymerization reaction be carried out in the presence of a solvent.The solvent has no particular restriction so long as it is inert to thereaction. Examples thereof include aromatic hydrocarbons such as benzeneand toluene, hydrocarbon halides such as methyl chloride, methylenechloride and 1,2-dichloroethane, nitro compounds such as nitromethaneand nitroethane, saturated hydrocarbons such as hexane, heptane, octaneand nonane, and mixed solvents thereof. The amount of the solvent to beused has no particular restriction, and is preferably 0.5 to 100 partsby weight per part by weight of the alkenyl ether monomer.

The temperature of the polymerization reaction has no particularrestriction, and is preferably −80 to 100° C.

The conversion from a polyalkenyl ether (copolymer) having acetals atits 2, 3, or 4 ends to a polyalkenyl ether (copolymer) having formylgroups at its 2, 3, or 4 ends by acid hydrolysis can be carried out inaccordance with, for example, a known method [Tetrahedron, 43, 825(1987), J. Org. Chem., 51, 567 (1986), JP-A-2001-11009, and the like].The final reduction treatment can be carried out by, for example, amethod in which reduction is carried out with hydrogen utilizing a metalcatalyst such as Raney nickel, or a method in which reduction is carriedout with boron hydride.

The method of acid hydrolysis is preferably a method in which heatingwith stirring is carried out in a mixed solvent of acetic acid andwater.

(2) Polyurethane (I)

Polyurethane (I) of the present invention can be produced in accodancewith known methods (U.S. Pat. No. 5,952,437, and the like) or inaccordance with the methods using, for example, Compound A and apolyisocyanate compound, and if required, other polyols, a chainextender, a polymerization stop agent, and the like as raw materials.

As polyisocyanate compounds, mention be made of the same ones as thosementioned above, and these be used alone or in mixture of two or morethereof.

As the other polyols, mention be made of ethylene glycol, propyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydroquinone,dimethylol propionic acid, dimethylol butanoic acid, trimethylolpropane,glycerin, and pentaerythritol, or polyester polyols obtained by allowingthese polyols to react with polybasic acids, polyether polyols such aspolytetramethylene ether glycol, polyethylene glycol, and polypropyleneglycol, polyolefin polyols such as polybutadiene polyol, hydrogenatedpolybutadiene polyol, and polyisopurene polyol, polycarbonate esterpolyol, polycaprolactone polyol, acryl polyol, and the like. Herein,examples of the polybasic acid include aliphatic dicarboxylic acids suchas succinic acid, glutaric acid, adipic acid, sebacic acid, fumaricacid, maleic acid, and maleic anhydride, or acid anhydrides thereof, andaromatic dicarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, 2,6-naphthalene dicarboxylic acid, dibenzoic acid,4,4-diphenylene dicarboxylic acid, ethylenebis(p-benzoic acid),1,4-tetramethylenebis(p-oxybenzoic acid), ethylenebis(p-oxybenzoicacid), and 1,3-trimethylenebis(p-oxybenzoic acid). Whereas, Polyurethane(I) obtainable using a polyol having an acidic group such asdimethylolpropionic acid or dimethylolbutanoic acid can be convert intoan aqueous polyurethane resin by neutralizaing the acidic group (such asa carboxy group)in accordance With known methods (JP-A-5-194836,JP-A-8-27242, JP-A-8-259884, and the like), or in accordance with themethods described therein, using an organic base such as ammonia,triethylamine, propylamine, dibutylamine, amylamine, 1-aminooctane,2-dimethyl aminoethanol, ethyl aminoethanol, 2-diethyl aminoethanol,1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol,1-dimethylamino-2-propanol, 3-dimethylamino-1-propanol, 2-propylaminoethanol, ethoxypropylamine, aminobenzyl alcohol, morpholine,piperidine, or piperazine, or an inorganic base such as sodiumhydroxide, potassium hydroxide, sodium carbonate, or potassium carbonateis preferably used in an amount of 0.5 to 1.5 equivalents (molar ratio)based on the amount of the acidic group to neutralize the acidic group.

When the other polyols are used, Compound A is contained therein in anamount of, preferably 5 wt % or more, and more preferably 20 wt % ormore based on the total amount of the polyol. However, when a hard onesuch as acryl polyol or isophthalic acid type polyester polyol is usedas the other polyols, Compound A is contained therein in an amount of,preferably 0.5 wt % or more, and more preferably 2 wt % or more based onthe total amount of the polyol.

As the chain extenders, low molecular weight polyols, diamines,alkanolamines, hydrazine, and the like are used.

Examples of the low molecular weight polyols include ethylene glycol,propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, hydroquinone, 2-ethyl-1,3-hexanediol,2-butyl-2-ethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol.

Examples of the diamines include ethylenediamine, propylenediamine,tetramethylenediamine, hexamethylenediamine, isophoronediamine, and1,4-cyclohexanediamine.

Examples of the alkanolamines include diethanolamine andtriethanolamine.

Examples of the polymerization stop agents include dialkylamines such asdibutylamine, amines having hydroxyl groups such as monoethanolamine anddiethanolamine, monoamine type amino acids such as glycine, alanine,glutamic acid and aminobutyric acid, alcohols such as ethanol and2-propanol, or mixtures thereof.

The ratio of the number of moles of the isocyanate group to the totalnumber of moles of the hydroxyl group and the amino group in the rawmaterial is preferably 0.1 to 10, further preferably 0.5 to 3, and morepreferably 0.8 to 2.

The reaction temperature is preferably 0 to 300° C.

For the production of Polyurethane (I) of the present invention, ifrequired, a solvent be used. Examples of the solvents include ketonessuch as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etherssuch as tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene,and xylene, and esters such ethyl acetate and butyl acetate. Whendiamines are used as chain extenders, alcohols such as methanol,ethanol, 2-propanol, and 1-butanol can also be used. These solvents areeach preferably used in an amount of 0.5 to 100 parts by weight per partby weight of the raw materials for Polyurethane (I).

Further, for the production of Polyurethane (I) of the presentinvention, if required, organometal catalysts such as tin octylate,tetrabutoxytitanium, and di-n-butyl tin dilaurate, catalysts of tertiaryamines such as triethylene diamine, and the like be used. In general,the amount thereof to be used is preferably 0.001 to 5 wt % based on theamount of the raw material for Polyurethane (I).

Polyurethane (I) of the present invention has no particular restrictionas to the weight-average molecular weight. When it is used as apolyurethane elastomer or the like, the weight-average molecular weightis preferably 30000 to 1000000, further preferably 30000 to 500000, andmore preferably 30000 to 300000. When Polyurethane (I) is used for ink,the weight-average molecular weight is preferably 1000 to 100000, andmore preferably 1000 to 30000.

Polyurethane (I) of the present invention having the above-mentionedweight-average molecular weight are excellent in flexibility,compatibility with low polarity resins, uniformity of composition,solubility, stickiness, bonding property, adhesion, electricalinsulation property, weather resistance, water resistance, transparency,thermal aging resistance, results in a pressure cooker test, and thelike.

Polyurethane (I) of the present invention further contains, if required,conventional additives such as a phenol type antioxidant, asulfur-having antioxidant, a phosphorous-having antioxidant, anultraviolet absorber, a hindered amine type photostabilizer, anantistatic agent, an inorganic colloid sol such as colloidal silica orcolloidal alumina, a silane coupling agent, a coloring agent, a waxagent, an antiseptic agent, an anti-foaming agent, a plasticizer, aslipping agent, a catalyst, a viscosity modifier, a leveling agent, ananti-gelling agent, a filler, a solvent, a film-forming aid, adispersant, a thickener, and a perfume is used. For example, whenPolyurethane (I) of the present invention as a polyurethane paint or alacquer, it further contain cellulose derivatives such as cellulosenitrate or cellulose acetate-propionate cellulose acetate-butylate.These additives be added during the production of Polyurethane (I).

Examples of a phenol type antioxidant include2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol,distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate,1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidamide], 4,4′-thiobis(6-tert-butyl-m-cresol),2,2′-methylenebis(4-methyl-6-tert-butylphenol),2,2′-methylenebis(4-ethyl-6-tert-butylphenol),4,4′-butylidenebis(6-tert-butyl-m-cresol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4-sec-butyl-6-tert-butylphenol),1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol,stearyl(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethyleneglycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester,bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate,1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane,3,9-bis{1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5.5]undecaneand triethylene glycolbis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

Examples of a sulfur-having antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristylthiodipropionate, and distearyl thiodipropionate, and β-alkylmercaptopropionic acid esters of polyol such as pentaerythritoltetra(β-dodecyl mercapto propionate).

Examples of a phosphorous-having antioxidant includetris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite,tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite,tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritoldiphosphite, tetra(tridecyl) isopropylidene diphenol diphosphite,tetra(tridecyl)-4,4′-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite,hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl)biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,2,2′-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite,2,2′-methylenebis (4,6-tert-butylphenyl)octadecyl phosphite,2,2′-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite,tris{2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl}amine,and a phosphite of 2-ethyl-2-butyl propylene glycol and2,4,6-tri-tert-butylphenol.

These antioxidants are each used in an amount of 0.001 to 10 parts byweight, and more preferably 0.05 to 5 parts by weight per 100 parts byweight of Polyurethane (I).

Examples of the ultraviolet absorber include 2-hydroxybenzophenones suchas 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octoxybenzophenone, and5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone);2-(2′-hydroxyphenyl)benzotriazoles such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-tert-octylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-dicumylphenyl)benzotriazole,2,2′-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, and2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole; benzoatessuch as phenyl salicylate, resorcinol monobenzoate,2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, andhexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilidessuch as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide;cyanoacrylates such as ethyl-α-cyano-β,β-diphenyl acrylate, andmethyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate; andtriaryltriazines such as2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine.

Examples of the hindered amine type photostabilizer include1-oxy-2,2,6,6-tetramethyl-4-piperidinol,1-hydroxy-2,2,6,6-tetramethyl-4-piperidinol,2,2,6,6-tetramethyl-4-piperidyl stearate,1,2,2,6,6-pentamethyl-4-piperidyl stearate,2,2,6,6-tetramethyl-4-piperidyl benzoate,bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane tetracarboxylate,tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,bis(2,2,6,6-tetramethyl-4-piperidyl)/di(tridecyl)-1,2,3,4-butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)/di(tridecyl)-1,2,3,4-butanetetracarboxylate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinatepolycondensates,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethanepolycondensates,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazinepolycondensates,1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazinepolycondensates,1,5,8,12-tetrakis{2,4-bis[N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]-s-triazin-6-yl}-1,5,8,12-tetraazadodecane,1,5,8,12-tetrakis{2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-s-triazin-6-yl}-1,5,8,12-tetraazadodecane,1,6,11-tris{2,4-bis[N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]-s-triazin-6-ylamino}undecane,and1,6,11-tris{2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-s-triazin-6-ylamino}undecane.

The ultraviolet absorber or the hindered amine type photostabilizer isused in an amount of preferably 0.001 to 30 parts by weight, and morepreferably 0.05 to 10 parts by weight per 100 parts by weight ofPolyurethane (I).

Polyurethane (I) of the present invention is useful for applicationssuch as paints, coating agents, inks, adhesives, photoresists, solderresists, shaping materials, sealing agents, or molding materials, or theraw materials therefore.

(2-1) Urethane Acrylate (II)

Urethane acrylate (II) of the present invention be produced by using,for example, Compound A, a polyisocyanate compound, and a hydroxylgroup-having acrylate represented by the formula (D):

(wherein R¹⁰, R¹¹, R¹² and R¹³ respectively have the same meanings asdefined above), and, if required, other polyols, diamines, and the likeas raw materials.

In this case, the ratio of the number of moles of the isocyanate groupto the number of moles of the hydroxyl group in the raw materials ispreferably 0.1 to 10, further preferably 0.5 to 3, and more preferably0.8 to 2.

As the polyisocyanate compounds, mention be made of the same ones asthose described above. These can be used alone, or in mixture of two ormore thereof.

Examples of the hydroxyl group-containing acrylate include2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and2-hydroxybutyl (meth)acrylate. In this specification, (meth)acrylatemeans acrylate or methacrylate, and other acrylic acid or methacrylicacid derivatives are also referred to in the same manner.

As the other polyols and the diamines, mention be made of the same onesas the other polyols and the diamines mentioned in the description of(2), respectively.

Urethane acrylate (II) of the present invention can be produced with aknown method such as a solution method or a melting method (a one-shotmethod, a prepolymer method, or the like).

The reaction temperature is preferably 50 to 100° C., and morepreferably 55 to 85° C.

It is preferable to add an inhibitor of radical polymerization for thepurpose of preventing the polymerization of vinyl groups, during thereaction. Examples of the inhibitor of radical polymerization includehydroquinone, hydroquinone monomethyl ether, and phenothiazine. Theseare each preferably used in an amount of 0.001 to 5 wt % based on theamount of the raw materials for Urethane acrylate (II).

When the reaction is effected with the solution method, a solvent isused, and as the solvents, mention be made of a radicalphotopolymerizable monomer, ketones such as methyl ethyl ketone andmethyl isobutyl ketone, ethers such as tetrahydrofuran and diethyleneglycol monoethyl ether acetate, aromatic hydrocarbons such as benzene,toluene and xylene, and the like.

Examples of the radical photopolymerizable monomer includemonofunctional compounds and multifunctional compounds. Examples of themonofunctional compounds include 2-hydroxyethyl (meth)acrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl(meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl(meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate,isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth.)acrylate,octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl(meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl(meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate,ethoxydiethylene glycol (meth)acrylate, benzyl (meth)acrylate,cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, polyethyleneglycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate,methoxy ethylene glycol (meth)acrylate, ethoxyethoxyethyl(meth)acrylate, methoxy polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadiene (meth)acrylate,dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate,tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, bornyl(meth)acrylate, diacetone (meth)acrylamide, isobutoxymethyl(meth)acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N,N-dimethyl(meth)acrylamide, tert-octyl (meth)acrylamide, dimethylaminoethyl(meth)acrylate, diethylaminoethyl (meth)acrylate,7-amino-3,7-dimethyloctyl (meth)acrylate, N,N-diethyl (meth)acrylamide,N,N′-dimethylaminopropyl (meth)acrylamide, (meth)acryloylmorpholine,maleic acid esters, and fumaric acid esters. The commercially availableproducts of the monofunctional compounds include ARONIX M111, M113,M114, and M117 (all produced by To a Gosei Kagaku Kogyo Co., Ltd.),KAYARAD TC110S, R629, and R644 (all produced by NIPPON KAYAKU Co.,Ltd.), VISCOAT 3700 (produced by Osaka Organic Chemistry Co., Ltd.), andthe like. Examples of the multifunctional compounds includetrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate,polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,trimethylolpropane trioxyethyl (meth)acrylate,tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate,tris(2-hydroxyethyl)isocyanurate di (meth)acrylate, tricyclodecanedimethanol di (meth)acrylate, epoxy(meth)acrylate obtained by theaddition of (meth)acrylate to diglycidyl ether of bisphenol A, andtriethylene glycol divinyl ether. The commercially available products ofthe multifunctional compounds include Yupimer UV SA1002 and SA2007 (allproduced by Mitsubishi Chemical Corp.), Viscoat 700 (produced by OsakaOrganic Chemical Industry Co., Ltd.), KAYARAD R-604, DPCA-20, DPCA-30,DPCA-60, DPCA-120, HX-620, D-310, and D-330 (all produced by NipponKayaku Co., Ltd.), ARONIX M-210, M-215, M-315, and M-325 (all producedby Toa Gosei Kagaku Kogyo Co., Ltd.), and the like.

Whereas, If required, a catalyst also be used for the reaction. As thecatalysts, mention be made of the same ones as the catalysts used forthe production of Polyurethane (I) mentioned in the description of (2).The amount of the catalyst to be used is preferably 0.001 to 5 wt %based on the amount of the raw materials of Urethane acrylate (II).

a composition having Urethane acrylate (II) and a radical photo-, orthermal polymerization initiator (which also be referred to hereinafteras Composition A) is obtained by mixing Urethane acrylate (II) of thepresent invention with a polymerization initiator generating radicalsthrough light irradiation or heating (radical photo-, or thermalpolymerization initiator), and if required, the radicalphotopolymerizable monomer, further, if required, other radicalphotopolymerizable polymers or oligomers, and the like.

For the preparation of Composition A, the order of addition of thesecomponents, the mixing method thereof, and the like have no particularrestriction.

As a the other radical photopolymerizable polymers or oligomers, mentionbe made of urethane (meth)acrylate other than the urethane acrylates ofthe present invention, polyester (meth)acrylate, epoxy (meth)acrylate,polyamide (meth)acrylate, polysiloxane having a (meth)acryloyloxy group.

The number-average molecular weight of Urethane acrylate (II) containesin Composition A is preferably 200 to 10000, and more preferably 500 to5000.

Example of the radical thermal polymerization initiators include azocompounds such as 2,2′-azobisisobutyronitrile,2,2′-azobis-2-methylbutyronitrile,2,2′-azobis-2,4-dimethylvaleronitrile,1,1′-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2′-azobisisobutyrate-,4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (2-amidinopropene)dihydrochloride, 2-tert-butylazo-2-cyanopropane,2,2′-azobis(2-methylpropionamide) dihydrate and2,2′-azobis(2,4,4-trimethylpentane), peroxy esters such as tert-butylperoxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxylaurate,tert-butyl peroxyisophthalate, tert-butyl peroxyacetate, tert-butylperoxyoctoate, and tert-butylperoxybenzoate, diacyl peroxides such asbenzoyl peroxide, hydroperoxides such as cumene hydroperoxide, methylethyl ketone peroxide, potassium persulfate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, dialkyl peroxides or peroxydicarbonates, hydrogen peroxide, and the like.

The content of the radical thermal polymerization initiator ispreferably 0.2 to 20 parts by weight, and more preferably 1 to 10 partsby weight per 100 parts by weight of Urethane acrylate (II).

Examples of the radical photopolymerization initiator include benzoinssuch as benzoin and benzoin methyl ether, benzophenones such asbenzophenone, methylbenzophenone, and 4,4′-dichlorobenzophenone, and4,4′-bisdiethyl aminobenzophenone, acetophenones such as acetophenone,2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone,1-hydroxycyclohexyl phenyl ketone, N,N-dimethyl aminoacetophenone and2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone,1-chloroanthraquinone, 2-amyl anthraquinone, and 2-amino anthraquinone,thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropyl thioxanthone and2-isopropyl thioxanthone, ketals such as acetophenone dimethyl ketal andbenzyl dimethyl ketal.

The content of the radical photopolymerization initiator is preferably0.2 to 20 parts by weight, and more preferably 1 to 10 parts by weightper 100 parts by weight of Urethane acrylate (II).

Composition A is cured through heating to 50 to 200° C. (when itcontains a radical thermal polymerization initiator), or throughirradiation with an infrared ray, a visible ray, an ultraviolet ray, anelectron beam, α, β, or γ ray, or the like (when it contains a radicalphotopolymerization initiator).

Composition A is useful for applications such as a coating agent, aphotoresist, or a solder resist.

The polyurethane obtainable from polymerization of Urethane acrylate(II) contained in the cured product resulting from curing of CompositionA is also included in the concept of the polyurethane of the presentinvention.

Urethane acrylate (II) of the present invention further contain therein,if required, conventional additives such as a cationicphotopolymerizable polymer/oligomer/monomer, a cationic photoinitiator,a phenol type antioxidant, a sulfur-having antioxidant, aphosphorous-having antioxidant, an ultraviolet absorber, a hinderedamine type photostabilizer, an antistatic agent, an inorganic colloidsol such as colloidal silica or colloidal alumina, a silane couplingagent, a coloring agent, a wax agent, an antiseptic agent, ananti-foaming agent, a plasticizer, a slipping agent, a catalyst, aviscosity modifier, a leveling agent, an anti-gelling agent, a filler, asolvent, a film-forming aid, a dispersant, a thickener, and a perfume.These additives be added when Urethane acrylate (II) is produced.

As the phenol type antioxidants, the sulfur-having antioxidants, thephosphorus-having antioxidants, the ultraviolet absorbers, and thehindered amine type photostabilizers, mention be made of the same onesas those mentioned in the description of (2).

Urethane acrylate (II) of the present invention is useful forapplications such as paints, coating agents, inks, adhesives, films,fibers, photoresists, solder resists, semiconductor sealing materials,laminated sheets, shaping materials, and sealing agents, or the like.Particularly, it is suitable for applications such as coating agents(particularly, a covering coating agent for an optical fiber) andadhesives.

(2-2) Urethane Alkenyl Ether (XI)

Urethane alkenyl ether (XI) of the present invention can be produced byusing, for example, Compound A, a polyisocyanate, and a hydroxylgroup-having alkenyl ether represented by formula (E):

(wherein R³⁴, R³⁵, R³⁶ and R³⁷ respectively have the same meanings asdefined above.), and if required, other polyols, diamine, and the like,as raw materials.

In this case, the ratio of the number of moles of the isocyanate groupto the number of moles of the hydroxyl group in the raw materials ispreferably 0.1 to 10, further preferably 0.5 to 3, and more preferably0.8 to 2.

As the polyisocyanates, mention be made of the same ones as thepolyisocyanates mentioned in the description of (2).

The hydroxyl group-having alkenyl ether is preferably a compoundobtained by the reaction of an alkyl or cycloalkyl compound having twoor more hydroxyl groups in the molecule, and acetylene. Examples thereofinclude 2-hydroxyethyl vinyl ether, 2-hydroxypropylvinyl ether,4-hydroxybutylvinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxybutylvinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinylether, 6-hydroxyhexyl vinyl ether, and cyclohexane dimethanol monovinylether.

As the other polyols and the diamines, mention be made of the same onesas the other polyols and the diamines mentioned in the description of(2), respectively.

Urethane alkenyl ether (XI) of the present invention can be producedwith a known method such as a solution method or a melting method (aone-shot method, a prepolymer method, or the like).

The reaction temperature is preferably 50 to 100° C., and morepreferably 55 to 85° C.

Although the solvents used in the solution method have no particularrestriction, mention be made of a cationic photopolymerizable monomer,ketones such as methyl ethyl ketone and methyl isobutyl ketone, etherssuch as tetrahydrofuran, aromatic hydrocarbons such as benzene, tolueneand xylene, and the like.

Examples of the cationic photopolymerizable monomer include an epoxygroup-having compound (a), a vinyl compound (b), a dicyclo ortho estercompound (c), a spiro ortho carbonate compound (d), and an oxetanering-having compound (e). There is no problem even if these are usedalone, or in combination of two or more thereof. Among the compounds (a)to (e), compounds (a) and (e) are particularly preferred to. Examples ofthe epoxy group-having compound (a) include3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate,bis-(3,4-epoxycyclohexyl)adipate,2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanone-m-dioxane,bis(2,3-epoxycyclopentyl) ether, limonene dioxide, 4-vinylcyclohexenedioxide, phenyl glycidyl ether, bisphenol type epoxy resins such asbisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenatedbisphenol A type epoxy resin, and brominated bisphenol A type epoxyresin, novolak type epoxy resins such as phenol novolak type epoxyresin, cresol novolak type epoxy resin, and brominated phenol/novolaktype epoxy resin, and polyglycidyl ethers of polyhydric alcohols.Examples of the vinyl compound (b) include styrenes such as styrene,α-methylstyrene, and p-chloromethylstyrene; alkyl vinyl ethers such asn-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, andhydroxybutyl vinyl ether; alkenyl vinyl ethers such as allyl vinyl etherand 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such asethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinylethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; alkyldivinyl ethers such as butanediol divinyl ether, triethylene glycoldivinyl ether, and cyclohexanediol divinyl ether; aralkyl divinyl etherssuch as 1,4-benzene dimethanol divinyl ether and m-phenylene bis(ethylene glycol) divinyl ether; aryl divinyl ethers such ashydroquinone divinyl ether and resorcinol divinyl ether. Examples of thedicyclo ortho ester compound (c) include1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2,2,2]octane and1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane. Examples ofthe spiro ortho carbonate compound (d) include1,5,7,11-tetraoxaspiro[5,5]undecane,3,9-dibenzyl-1,5,7,11-tetraoxaspiro[5,5]undecane,1,4,6-trioxaspiro[4,4]nonane, and 1,4,6-trioxaspiro[4,5]decane. Examplesof the oxetane ring-having compound (e) include 3,3-dimethyl oxetane,3,3-bis(chloromethyl) oxetane, 2-hydroxymethyl oxetane,3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyl oxetane,3-ethyl-3-phenoxymethyl oxetane, resorcinol bis(3-methyl-3-oxetanylethyl) ether, and m-xylylenebis(3-ethyl-3-oxetanyl ethyl ether). Thesecompounds are used alone, or in combination of two or more thereof.

Further, for the urethanization reaction, if required, organometalcatalysts such as tin octylate, dibutyltin dilaurate, andtetrabutoxytitanium and urethanization catalysts of tertiary amines suchas triethylenediamine be used. The amount thereof to be used ispreferably 0.001 to 5 wt % based on the amount of the reaction solution.

A composition having Urethane alkenyl ether(XI) and a polymerizationinitiator generating an acid through heating or light irradiation (whichalso be referred to hereinafter as Composition B) can be obtained bymixing urethane alkenyl ether(XI) of the present invention with apolymerization initiator generating an acid through heating or lightirradiation, if required, the cationic photopolymerizable monomer, andfurther, if required, other cationic photopolymerizable polymers oroligomers, and the like. For the preparation of Composition B, the orderof addition of these components, the mixing method thereof, and the likehave no particular restriction.

The number-average molecular weight of Urethane alkenyl ether (XI) foruse in Composition B is preferably 200 to 10000, and more preferably 500to 5000.

As the polymerization initiators generating an acid through heating,mention be made of a compound obtained by neutralizing a Bronsted acidor a Lewis acid with a Lewis base, a complex compound comprising a Lewisacid and a Bronsted acid, a complex compound comprising a Lewis acid anda Bronsted base, sulfonic acid esters, phosphoric acid esters, oniumcompounds, and the like.

Examples of the Bronsted acid include sulfuric acid, sulfonic acid,acetic acid, phosphoric acid, boric acid, and carboxylic acid, andderivatives thereof, and preferred are alkylbenzenesulfonic acid having1 to 50 carbon atoms such as dodecylbenzenesulfonic acid, mono-, ordi-halogenocarboxylic acids having 1 to 50 carbon atoms such aschloroacetic acid and dichloroacetic acid, phosphoric acid mono-, ordi-esters having 1 to 50 carbon atoms such as monomethyl phosphate anddimethyl phosphate, and the like. These Bronsted acids can be usedalone, or in combination of two or more thereof.

As the Lewis acid, preferred are metal halides and organometalliccompounds, and specific examples thereof include metal halides such asboron trifluoride, aluminum trichloride, titanous chloride, titanicchloride, ferrous chloride, ferric chloride, zinc chloride, zincbromide, stannous chloride, stannic chloride, stannous bromide, andstannic bromide, and organometallic compounds such as trialkyl boron,trialkyl aluminum, dialkyl aluminum halide, monoalkyl aluminum halide,tetraalkyl tin, aluminum acetyl acetonate, iron acetyl acetonate,zirconium acetyl acetonate, dibutyltin acetyl acetonate, dibutyltindilaurate, dioctyltin ester maleate, magnesium naphthenate, calciumnaphthenate, manganese naphthenate, iron naphthenate, cobaltnaphthenate, copper naphthenate, zinc naphthenate, zirconiumnaphthenate, lead naphthenate, calcium octylate, manganese octylate,iron octylate, cobalt octylate, zinc octylate, zirconium octylate, tinoctylate, lead octylate, zinc laurate, magnesium stearate, aluminumstearate, calcium stearate, cobalt stearate, zinc stearate, and leadstearate. These Lewis acids can be used alone or in combination of twoor more thereof.

Examples of the Lewis base include amines such as ammonia,triethylamine, pyridine, aniline, morpholine, N-methylmorpholine,pyrrolidine, N-methylpyrrolidine, piperidine, N-methylpiperidine,cyclohexylamine, N-butylamine, dimethyloxazoline, imidazole,N-methylimidazole, N,N-dimethyl ethanolamine, N,N-diethyl ethanolamine,N,N-dimethyl isopropanolamine, N,N-diethyl isopropanolamine,N,N-dipropyl isopropanolamine, N,N-dibutyl isopropanolamine, N-methyldiethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-butyldiethanolamine, N-methyl diisopropanolamine, N-butyl diisopropanolamine,triethanolamine, triisopropanolamine, and tri-sec-butanolamine; amidecompounds such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methylpyrrolidone, and hexamethylphosphoric acid triamide; sulfoxidecompounds such as dimethylsulfoxide; ether compounds such as diethylether and tetrahydrofuran; thioether compounds such as dimethyl sulfide;phosphoric acid ester compounds such as trimethyl phosphate, triethylphosphate, and tributyl phosphate; boric acid ester compounds such astrimethyl borate; carboxylic acid ester compounds such as ethyl acetateand butyl acetate; carbonic acid ester compounds such as ethylenecarbonate; and trialkyl phosphine compounds such as tributyl phosphine.

The ratio of the basic activity of the Lewis base to the acidic activityof the Bronsted acid or the Lewis acid is preferably 0.1 to 10.

The content of the polymerization initiator generating an acid throughheating is preferably 0.01 to 10 parts by weight, and more preferably0.02 to 5 parts by weight per 100 parts by weight of Urethane alkenylether (XI).

Composition B having a polymerization initiator generating an acidthrough heating is generally cured through heating at 50 to 200° C. for2 minutes to 10 hours.

As the polymerization initiator generating an acid through lightirradiation, mentioned are an onium salt compound, a sulfone compound, asulfonic acid ester compound, a sulfonimide compound, a diazosulfonecompound, a disulfonyl methane compound, a nitrobenzyl compound, and anaphthoquinone diazide compound.

Examples of the onium salt compound include an iodonium salt, asulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt,and a pyridium salt. Specific examples thereof includebis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate,bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate,bis(4-tert-butylphenyl)iodonium-2-trifluoromethylbenzene sulfonate,bis(4-tert-butylphenyl)iodonium-10-camphorsulfonate,bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, diphenyliodoniumtrifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate,diphenyliodonium-2-trifluoromethylbenzene sulfonate,diphenyliodonium-10-camphorsulfonate,diphenyliodonium-p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutane sulfonate,triphenylsulfonium-2-trifluoromethylbenzene sulfonate,triphenylsulfonium-10-camphorsulfonate,triphenylsulfonium-p-toluenesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluorobutane sulfonate, 4-tert-butylphenyldiphenylsulfonium-2-trifluoromethylbenzene sulfonate, 4-tert-butylphenyldiphenylsulfonium-10-camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium-p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium trifluoromethane sulfonate, 4-tert-butoxyphenyldiphenylsulfonium nonafluorobutane sulfonate, 4-tert-butoxyphenyldiphenylsulfonium-2-trifluoromethylbenzene sulfonate,4-tert-butoxyphenyl diphenylsulfonium-10-camphorsulfonate, and4-tert-butoxyphenyl diphenylsulfonium-p-toluene sulfonate.

Examples of the sulfone compound include β-ketosulfone and β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples thereofinclude phenacylphenylsulfone, mesitylphenacylsulfone,bis(phenylsulfonyl)methane, and 4-tris(phenacyl)sulfone.

Examples of the sulfonic acid ester compound include alkyl sulfonic acidester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, andiminosulfonate. Specific examples thereof include benzoin tosylate,pyrogallol tris(trifluorosulfonate), pyrogallol methane sulfonic acidtriester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate,α-methylolbenzoin octanesulfonate, α-methylolbenzointrifluoromethanesulfonate, and α-methylolbenzoin dodecylsulfonate.

Examples of the sulfonimide compound includeN-(trifluoromethylsulfonyloxy)succinimide,N-(trifluoromethylsulfonyloxy)phthalimide,N-(trifluoromethylsulfonyloxy)diphenylmaleimide,N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-dioxy-2,3-dicarboxyimide,N-(trifluoromethylsulfonyloxy)naphthylimide,N-(camphorsulfonyloxy)succinimide, N-(camphorsulfonyloxy)phthalimide,N-(camphorsulfonyloxy)diphenylmaleimide,N-(camphorsulfonyloxy)dicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-dioxy-2,3-dicarboxyimide,N-(camphorsulfonyloxy)naphthylimide,N-(4-methylphenylsulfonyloxy)succinimide,N-(4-methylphenylsulfonyloxy)phthalimide,N-(4-methylphenylsulfonyloxy)diphenylmaleimide,N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-dioxy-2,3-dicarboxyimide,N-(4-methylphenylsulfonyloxy)naphthylimide,N-(2-trifluoromethylphenylsulfonyloxy)succinimide,N-(2-trifluoromethylphenylsulfonyloxy)phthalimide,N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide,N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-trifluoromethylphenylsulfonyloxy)-7-bxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-dioxy-2,3-dicarboxymide,N-(2-trifluoromethylphenylsulfonyloxy)naphthylimide,N-(4-fluorophenylsulfonyloxy)succinimide,N-(4-fluorophenylsulfonyloxy)phthalimide,N-(4-fluorophenylsulfonyloxy)diphenylmaleimide,N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide,N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyimide,and N-(4-fluorophenylsulfonyloxy)naphthylimide.

The polymerization initiators generating an acid through lightirradiation can be used alone, or in combination of two or more thereof.The content thereof is preferably 0.01 to 50 parts by weight, morepreferably 0.1 to 30 parts by weight, and further preferably 0.5 to 25parts by weight per 100 parts by weight of Urethane alkenyl ether (XI).

Composition B having the polymerization initiator generating an acidthrough light irradiation is cured through irradiation with an infraredray, a visible ray, an ultraviolet ray, an electron beam, α, β, or γray, or the like.

A composition having Urethane alkenyl ether (XI) and a compound having amaleimido group (which also be referred to hereinafter as Composition C)can be obtained by mixing Urethane alkenyl ether (XI) of the presentinvention and a compound having a maleimido group. For the preparationof Composition C, the order of addition of these components, the mixingmethod thereof, and the like have no particular restriction.

The number-average molecular weight of Urethane alkenyl ether (XI) foruse in Composition C is preferably 200 to 10000, and more preferably 500to 5000.

The compound having a maleimido group has no particular restriction solong as it is a compound having one or more maleimido groups in themolecule, and examples thereof include aliphatic maleimide compoundssuch as N-methylmaleimide, N-butylmaleimide, N-hydroxyethylmaleimide,2,2,4-trimethylhexamethylene dimaleimide and2,4,4-trimethylhexamethylene dimaleimide, aromatic maleimide compoundssuch as N-(methoxyphenyl)maleimide, 4,4-diphenylmethane bismaleimide andN,N′-xylylene bismaleimide, and cyclic ring-having maleimide compoundssuch as N-cyclohexylmaleimide and methylenebis(4-N-cyclohexylmaleimide).

In Composition C, the ratio of the number of moles of the maleimidogroup to the number of moles of Urethane alkenyl ether (XI) ispreferably 0.001 to 3.0, and more preferably 0.5 to 1.5.

Composition C is cured through irradiation with an infrared ray, avisible ray, an ultraviolet ray, an electron beam, α, β, or γ ray, orthe like. In this step, Composition C also be mixed with a radicalphotopolymerization initiator. Alternatively, composition C is alsocured by being mixed with a radical thermal polymerization initiator,and being heated to 50 to 200° C.

As the radical photopolymerization initiators and the radical thermalpolymerization initiators, mention be made of the same ones as theradical photopolymerization initiators and the radical thermalpolymerization initiators for use in the production of Urethane acrylate(II), mentioned in the description of (2-1), respectively.

Urethane alkenyl ether (XI) of the present invention further contain, ifrequired, conventional additives such as a radical photopolymerizablepolymer/oligomer/monomer, a radical photoinitiator, a phenol typeantioxidant, a sulfur-having antioxidant, a phosphorous-havingantioxidant, an ultraviolet absorber, a hindered amine typephotostabilizer, an antistatic agent, an inorganic colloid sol such ascolloidal silica or colloidal alumina, a silane coupling agent, acoloring agent, a wax agent, an antiseptic agent, an anti-foaming agent,a plasticizer, a slipping agent, a catalyst, a viscosity modifier, aleveling agent, an anti-gelling agent, a filler, a solvent, afilm-forming aid, a dispersant, a thickener, and a perfume. Theseadditives may be added during the production of Urethane alkenyl ether(XI).

As the phenol type antioxidants, the sulfur-having antioxidants, thephosphorus-having antioxidant, the ultraviolet absorbers, and thehindered amine type photostabilizers, mention be made of the same onesas those mentioned in the description of (2).

Compositions B and C are useful for applications such as a coatingagent, a photoresist, and a solder resist.

The polyurethane obtainable from polymerization of Urethane alkenylether (XI) contained in each cured product resulting from curing ofCompositions B and C is also included in the concept of the polyurethaneof the present invention.

(3) Polyester (III)

Polyester (III) of the present invention can be produced, for example,using Compound A [preferably the compound represented by formula (A),wherein X is a hydrogen atom], a polybasic acid, and if required, otherpolyols, an animal or vegetable oil fatty acid, an animal or vegetableoil, and the like as raw materials with known methods (U.S. Pat. No.6,143,840, and the like), or similar methods thereto. The amount of thepolybasic acid to be used is preferably 10 to 80 wt %, and morepreferably 25 to 60 wt % based on the total amount of the raw.materials. The amount of the alcohol components (Compound A and theother polyols) to be used is preferably 10 to 80 wt %, andmorepreferably25 to 60 wt % based on the total amount of the raw materials.

The ratio of the number of moles of the hydroxyl group to the number ofmoles of the carboxyl group in the raw materials is preferably 0.8 to1.5, and more preferably 0.9 to 1.3.

As the polybasic acids, mention may be made of the same ones as thepolybasics mentioned in the description of (2).

As the other polyols, mention may be made of the same ones as thepolyols mentioned in the description of (2). When the other polyols areused, Compound A is contained in an amount of preferably 5% (molarratio) or more, and more preferably 20% (molar ratio) or more based onthe amount of the alcohol components in the raw materials.

Examples of the animal or vegetable oil fatty acid include soybean oilfatty acid, safflower oil fatty acid, tall oil fatty acid, linseed oilfatty acid, dehydrated castor oil fatty acid, and tung oil fatty acid.

Examples of the animal or vegetable oil include soybean oil, saffloweroil, linseed oil, dehydrated castor oil, and tung oil.

When the animal or vegetable oil fatty acid or the animal or vegetableoil is used, it is each preferably used in an amount of 20 wt % or lessbased on the total amount of the raw materials.

The weight-average molecular weight of Polyester (III) of thepresent,invention has no particular restriction. It is preferably 30000to 1000000, further preferably 30000 to 500000, and more preferably30000 to 300000 when Polyester (III) is used as a polyester elastomer,etc.

Polyesters (III) of the present invention having the above-mentionedweight-average molecular weight is excellent in flexibility,compatibility with low polarity resins, uniformity of composition,mechanical strength, solubility, stickiness, bonding property, adhesion,electrical insulation property, weather resistance, water resistance,transparency, thermal aging resistance, oil resistance, moldability ininjection molding, results in a pressure cooker test, and the like.

Polyester (III) of the present invention further contain, if required,conventional additives such as a phenol type antioxidant, asulfur-having antioxidant, a phosphorous-having antioxidant, anultraviolet absorber, a hindered amine type photostabilizer, anantistatic agent, an inorganic colloid sol, such as colloidal silica orcolloidal alumina, a silane coupling agent, a coloring agent, a waxagent, an antiseptic agent, an anti-foaming agent, a plasticizer, aslipping agent, a catalyst, a viscosity modifier, a leveling agent, ananti-gelling agent, a filler, a solvent, a film-forming aid, adispersant, a thickener, and a perfume, to be used. These additives maybe added during the production Polyester (III).

As the phenol type antioxidant, the sulfur-having antioxidant, thephosphorous-having antioxidant, the ultraviolet absorber, and thehindered amine type photostabilizer, mention may be made of the sameones mentioned in the description of (2).

A composition obtained by mixing Polyester (III) of the presentinvention with an amino resin (such as an urea resin, a melamine resin,or a guanamine resin obtainable by allowing urea, melamine, guanamine,or the like to react with formaldehyde) is useful for a paint, a coatingagent, an adhesive, or the like. The amount of the amino resin to beused is preferably 5 to 60 parts by weight per 100 parts by weight ofPolyester (III). When the composition [composition having Polyester(III) and an amino resin] is used for a paint, or the like, it mayfurther contain, if required, a dispersant, a wetting agent, ananti-settling agent, a segregation inhibitor, an anti-skinning agent, anantistatic agent, an antimould, a fire-retarding agent, and the like,each in an amount of 0.01 to 5 wt %. As an article to be coated, mentionbe made of metal, wood, plastic, inorganic material, concrete, asphalt,or the like. The above composition can be cured by drying under ordinarytemperature or by drying under heating.

(3-1) Ester Acrylate(IV)

Ester acrylate (IV) of the present invention can be obtained by allowingCompound A [preferably the compound represented by the formula(A), whereX is a hydrogen atom] or Polyester (III)(preferably, number-averagemolecular weight 100 to 5000) to react with acrylic acids or estersthereof, acryloyl chloride, or the like.

Examples of the acrylic acids include acrylic acids and methacrylicacids.

Examples of esters of the acrylic acids include methyl (meth)acrylate,ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate,2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl(meth)acrylate, phenoxyethyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-butoxyethyl (meth)acrylate, benzyl (meth)acrylate, andethylcarbitol (meth)acrylate.

Examples of the acryloyl chloride include acrylic acid chloride andmethacrylic acid chloride.

In the raw materials, the acrylic acids or esters thereof, acryloylchlorides, or the like are preferably used in an amount of 0.9 to 10equivalents (molar ratio) based on the amount of Compound A or Polyester(III), and the reaction temperature is preferably 0 to 70° C.

Ester acrylate (IV) of the present invention is cured by thermalpolymerization (preferably, at 50 to 200° C.).

A composition having Ester acrylate (IV) and a radical photo-, orthermal polymerization initiator (which also be referred to hereinafteras Composition D) can be obtained by mixing Ester acrylate (IV) of thepresent invention with a radical photo-, or thermal polymerizationinitiator, and if required, the radical photopolymerizable monomersmentioned in the description of (2-1), and further, if required, otherradical photopolymerizable polymers or oligomers, and the like. For thepreparation of Composition D, the order of addition of these components,the mixing method thereof, and the like have no particular restriction.

The number-average molecular weight of Ester acrylate (IV) inComposition D is preferably 200 to 10000, and more preferably 500 to5000.

As the radical photo-, or thermal polymerization initiators, mention bemade of the same ones as those mentioned in the description of (2-1).

The content of the radical photo-, or thermal polymerization initiatorsis the same as the content in (2-1).

The curing conditions for Composition D are the same conditions as thecuring conditions for Composition A in (2-1).

Ester acrylate (IV) of the present invention further contain, ifrequired, conventional additives such as a cationic photopolymerizablepolymer/oligomer/monomer, a cationic photoinitiator, a phenol typeantioxidant, a sulfur-having antioxidant, a phosphorous-havingantioxidant, an ultraviolet absorber, a hindered amine typephotostabilizer, an antistatic agent, an inorganic colloid sol such ascolloidal silica or colloidal alumina, a silane coupling agent, acoloring agent, a wax agent, an antiseptic agent, an anti-foaming agent,a plasticizer, a slipping agent, a catalyst, a viscosity modifier, aleveling agent, an anti-gelling agent, a filler, a solvent, afilm-forming aid, a dispersant, a thickener, and a perfume. Theseadditives be added during the production of Ester acrylate (IV).

As the phenol type antioxidants, the sulfur-having antioxidants, thephosphorus-having antioxidant, the ultraviolet absorbers, and thehindered amine type photostabilizers, mention be made of the same onesas, those mentioned in the description of (2).

Composition D is cured through heating to 50 to 200° C. (when itcontains a radical thermal polymerization initiator), or throughirradiation with an infrared ray, a visible ray, an ultraviolet ray, anelectron beam, α, β, or γ ray, or the like (when it contains a radicalphotopolymerization initiator).

Composition D is useful for applications such as a coating agent, aphotoresist, or a solder resist.

The polyester obtained from polymerization of Ester acrylate (IV)contained in the cured product resulting from curing of Composition D isalso included in the concept of the polyester of the present invention.

(4) Alkenyl Ether (V)

Alkenyl ether (V) of the present invention can be obtained by, forexample, subjecting Compound A and an alkenyl ether monomer to an etherexchange reaction with a known method [Tetrahedron, 28, 233-238 (1972)],or a similar method thereto.

As the alkenyl ether monomers, mention be made of the same ones as thosementioned in the description of (1).

The ratio of the number of moles of the alkenyl ether monomer to thenumber of moles of the hydroxyl group in the raw materials is preferably1 to 50.

A catalyst may be used, if required, during the production of Alkenylether (V) of the present invention, and a catalyst having palladium ispreferred to.

As the catalyst containing palladium, mentioned are palladium chloride,palladium acetate, palladium nitrate, palladium oxide, and palladiumcomplex, among which, a palladium complex is preferred. Examples of thepalladium complex include bis(acetonitrile)dichloropalladium,bis(benzonitrile)dichloropalladium,diaceto(1,10-phenanthroline)palladium,diaceto(2,2′-bipyridine)palladium, diaceto(ethylenediamine)palladium,diaceto(2,4-pentanediamine)palladium,diaceto(1,2-cyclohexanediamine)palladium,dichloro(1,10-phenanthroline)palladium,dichloro(2,2′-bipyridine)palladium, dichloro(ethylenediamine)palladium,dichloro(2,4-pentanediamine)palladium, anddichloro(1,2-cyclohexanediamine)palladium. These palladium complexesalso be the ones each formed in a reaction system by, for example, apalladium compound such as palladium chloride and a ligand such as1,10-phenanthroline.

The amount of the catalyst having palladium to be added is preferably0.0001 to 0.2 mole per mole of the alkenyl ether monomer.

The reaction may also be effected in the presence of a solvent. Examplesof the solvent include aromatic hydrocarbons such as toluene and xylene,aliphatic hydrocarbons such as heptane, hexane, cyclohexane, andheptane, ethers such as diethyl ether and diisopropyl ether, ketonessuch as acetone and methyl ethyl ketone, hydrocarbon halides such aschloroform, methylene chloride, and dichloroethane, and polar solventssuch as dimethyl formamide and dimethyl sulfoxide.

The reaction temperature is preferably −40 to 150° C.

A composition having Alkenyl ether (V) and a polymerization initiatorgenerating an acid through heating or light irradiation (which also bereferred to hereinafter as Composition E)can be obtained by mixingAlkenyl ether (V) with a polymerization initiator generating an acidthrough heating or light irradiation, and if required, the cationicphotopolymerizable monomer mentioned in the description of (2-2), andfurther, if required, other cationic photopolymerizable polymers oroligomers,.and the like. For the preparation of Composition E, the orderof addition of these components, the mixing method thereof, and the likehave no particular restriction.

The number-average molecular weight of Alkenyl ether (V) for use inComposition E is preferably 200 to 10000, and more preferably.500 to5000.

As the polymerization initiators generating an acid through heating orlight irradiation, mention be made of the same ones as those mentionedin the description of (2-2).

The content of the polymerization initiator generating an acid throughheating or light irradiation is the same as the content in (2-2).

The curing conditions for Composition E are the same conditions as thecuring conditions for Composition B′ in (2-2).

A composition having Alkenyl ether(V) and a compound having a male imidogroup (which also be referred to hereinafter as Composition F) can beobtained by moxing alkenyl ether (V) of the present invention and acompound having a maleimido group.

For the preparation of Composition F, the order of addition of thesecomponents, the mixing method thereof, and the like have no particularrestriction.

The number-average molecular weight of Alkenyl ether (V) in CompositionF is preferably 200 to 10000, and more preferably 500 to 5000.

As the compound having a maleimido group, mention be made of the sameones as those mentioned in the description of (2-2).

In Composition F, the ratio of the number of moles of the maleimidogroup to the number of moles of Alkenyl ether (V) is preferably 0.001 to3.0, and more preferably 0.5 to 1.5.

Composition F is cured through irradiation with an infrared ray, avisible ray, an ultraviolet ray, an electron beam, α, β, or γ ray, orthe like. In this step, Composition F may also be mixed with a radicalphotopolymerization initiator. Alternatively, composition F is cured bybeing mixed with a radical thermal polymerization initiator, and beingheated to 50 to 200° C.

As the radical photopolymerization initiators and the radical thermalpolymerization initiators, mention may be made of the same ones as thosementioned in the description of (2-1), respectively.

Alkenyl ether (V) of the present invention further contain, therein, ifrequired, conventional additives such as a radical photopolymerizablepolymer/oligomer/monomer, a radical photoinitiator, a phenol typeantioxidant, a sulfur-having antioxidant, a phosphorous-havingantioxidant, an ultraviolet absorber, a hindered amine typephotostabilizer, an antistatic agent, an inorganic colloid sol such ascolloidal silica or colloidal alumina, a silane coupling agent, acoloring agent, a wax agent, an antiseptic agent, an anti-foaming agent,a plasticizer, a slipping agent, a catalyst, a viscosity modifier, aleveling agent, an anti-gelling agent, a filler, a solvent, afilm-forming aid, a dispersant, a thickener, and a perfume. Theseadditives may be added during the production of Alkenyl ether (V).

As the phenol type antioxidants, the sulfur-having antioxidants, thephosphorus-having antioxidant, the ultraviolet absorbers, and thehindered amine type photostabilizers, mention be made of the same onesas those mentioned in the description of (2).

Compositions E and F are useful for applications such as a coatingagent, a photoresist, and a solder resist.

(5) Epoxy Resin, Epoxy Acrylate

An epoxy resin having a structural unit represented by formula (VII)

(wherein n, R¹, R², R³, R⁴and R⁵respectively have the same meanings asdefined above) can be obtained by allowing Compound A to react withepichlorohydrin by a known method. Hereinafter, the epoxy resin may alsobe referred to as Epoxy resin (VII).

A composition having Epoxy resin (VII) and a polymerization initiatorgenerating an acid through heating or light irradiation (which also bereferred to hereinafter as Composition G) can be obtained by mixingEpoxy resin (VII) is mixed with a polymerization initiator generating anacid through heating or light irradiation, and if required, the cationicphotopolymerizable monomer mentioned in the description of (2-2), andfurther, if required, other cationic photopolymerizable polymers oroligomers, and the like. For the preparation of Composition G, the orderof addition of these components, the mixing method thereof, and the likehave no particular restriction.

The number-average molecular weight of Epoxy resin (VII) in CompositionG is preferably 200 to 10000, and more preferably 500 to 5000.

As the polymerization initiators generating an acid through heating orlight irradiation, mention be made of the same ones as those mentionedin the description of (2-2).

The content of the polymerization initiator generating an acid throughheating or light irradiation is the same as the content in (2-2).

The curing conditions for Composition G are the same conditions as thecuring conditions for Composition B in (2-2).

An epoxy acrylate having a structural unit represented by the formula(VIII):

(wherein n, R¹, R², R³, R⁴ and R⁵ respectively have the same meanings asdefined above; and R²⁵, R²⁶, and R²⁷ are the same or different, and eachrepresents a hydrogen atom, a substituted or unsubstituted lower alkyl,a substituted or unsubstituted cycloalkyl, a substituted orunsubstituted aryl, or a substituted or unsubstituted aralkyl) can beobtained by allowing Epoxy resin (VII) to react with acrylic acids inthe presence of 2-ethyl imidazole, triethylbenzyl ammonium, and thelike, preferably at 50 to 130° C. Herein, as the substituted orunsubstituted lower alkyl, the substituted or unsubstituted cycloalkyl,the substituted or unsubstituted aryl, and the substituted orunsubstituted aralkyl, mention be made of the same ones as thosementioned above.

Hereinafter, the epoxy acrylate having the structural unit representedby formula (VIII) may also be referred to as Epoxy acrylate (VIII).

As the acrylic acids, mention be made of the same ones as thosementioned in the description of (3-1).

In the raw materials, the amount of acrylic acids to be used ispreferably 0.9 to 10 equivalents (molar ratio) based on the amount ofEpoxy resin (VII), and the reaction temperature is preferably 0 to 70°C.

A composition having Epoxy acrylate (VIII) and a radical photo-, orthermal polymerization initiator (which also be referred to hereinafteras Composition H) can be obtained by mixing epoxy acrylate (VIII) ismixed with a radical photo-, or thermal polymerization initiator. Forthe preparation of Composition H, the order of addition of thesecomponents, the mixing method thereof, and the like have no particularrestriction.

The number-average molecular weight of Epoxy acrylate (VIII) for use inComposition H is preferably 200 to 10000, and more preferably 500 to5000.

As the radical photo-, or thermal polymerization initiator, mention bemade of the same ones as those mentioned in the description of (2-1).

Epoxy acrylate (VIII) incorporate further contain, if required,conventional additives such as a cationic photopolymerizablepolymer/oligomer/monomer, a cationic photoinitiator, a phenol typeantioxidant, a sulfur-having antioxidant, a phosphorous-havingantioxidant, an ultraviolet absorber, a hindered amine typephotostabilizer, an antistatic agent, an inorganic colloid sol such ascolloidal silica or colloidal alumina, a silane coupling agent, acoloring agent, a wax agent, an antiseptic agent, an anti-foaming agent,a plasticizer, a slipping agent, a catalyst, a viscosity modifier, aleveling agent, an anti-gelling agent, a filler, a solvent, afilm-forming aid, a dispersant, a thickener, and a perfume. Theseadditives may be added during the production of Epoxy acrylate (VIII).

As the phenol type antioxidants, the sulfur-having antioxidants, thephosphorus-having antioxidant, the ultraviolet absorbers, and thehindered amine type photostabilizers, mention be made of the same onesas those mentioned in the description of (2).

Composition H is cured through heating to 50 to 200° C. (when itcontains a radical thermal polymerization initiator), or throughirradiation with an infrared ray, a visible ray, an ultraviolet ray, anelectron beam, α, β, or γ ray, or the like (when it contains a radicalphotopolymerization initiator).

Composition H is useful for applications such as a coating agent,.aphotoresist, and a solder resist.

BEST MODE FOR CARRYING OUT THE PRESENT INVENTION

The present invention is described below in more detail by referring toExamples, Comparative Examples, and Reference Examples.

REFERENCE EXAMPLE 1 Polyethyl Vinyl Ether (a) having Hydroxyl Groups atits Both Ends (Compound A wherein R¹ is Ethyl, and R², R³, R⁴, R⁵ and Xare a Hydrogen Atom

Into a 1-L flask made of glass, 28.9 g of ethyl orthoformate, 250 g oftoluene and 0.13 g of boron trifluoride diethyl ether complex wereadded. While stirring this solution at 20° C., 361 g of ethyl vinylether was added. The addition of ethyl vinyl ether startedpolymerization. After completion of the addition, the reaction mixturewas washed with a sodium hydroxide aqueous solution and distilled water.Then, the solvent was distilled off to obtain 370 g (yield 94.9%) ofpolyethyl vinyl ether having acetals at its both ends. Into a 2-L flaskmade of glass, 360 g of the resultant polyethyl vinyl ether havingacetals at its both ends, 430 g of acetic acid, and 250 g of water wereadded, and stirred at 60° C. for 3 hours. The reaction mixture wasneutralized with a saturated soda solution, and extracted with ethylacetate. Then, ethyl acetate was distilled off to obtain 320 g ofpolyethyl vinyl ether having formyl groups at its both ends. Into a 1-Lautoclave made of SUS, 130 g of the resultant polyethyl vinyl etherhaving formyl groups at its both ends, 420 g of ethanol, and 19.5 g ofRaney nickel were added, and hydrogen (1961 kPa) was introduced. Theautoclave was heated to 80° C., and stirring was carried out for 4hours. After the reaction, Raney nickel was filtered off, and then thesolvent was distilled off to obtain 114 g of Polyethyl vinyl ether (a)having hydroxyl groups at its both ends.

The molecular characteristics of the resultant Polyethyl vinyl ether ahaving hydroxyl groups at its both ends are shown in Table 1. Thenumber-average molecular weight of the polyethyl vinyl ether havinghydroxyl groups at its both ends was measured by means of gel permeationchromatography (GPC).

(GPC Analysis Conditions)

Column: TSKgel SuperHM-L, TSKgel SuperHM-M, and TSKgel SuperHM-N(manufactured by TOSOH CORPORATION Ltd.) were connected in series.

Mobile phase: Tetrahydrofuran (Flow rate: 1 ml/min)

Column oven: 40° C.

Detector:RI[RI-8000 (manufactured by TOSOH CORPORATION Ltd.)] TABLE 1Polyethyl vinyl ether Hydroxyl Water having hydroxyl groups valuecontent Number-average at its both ends (mgKOH/g) (ppm) molecular weight(a) 62.6 82 1,915

REFERENCE EXAMPLE 2 Polyisobutyl Vinyl Ether (b) having Hydroxyl Groupsat its Both Ends (Compound A wherein R¹ is Isobutyl, and R², R³, R⁴ andR⁵ are Each a Hydrogen Atom

Into a 1-L flask made of glass, 25.3 g of ethyl orthoformate, 250 g oftoluene, and 0.13 g of boron trifluoride diethyl ether complex wereadded. While stirring this solution at 20° C., 344 g of isobutyl vinylether was added. The addition of isobutyl vinyl ether startedpolymerization. After completion of the addition, the reaction mixturewas washed with a sodium hydroxide aqueous solution and distilled water.Then, the solvent was distilled of f to obtain 355 g of polyisobutylvinyl ether having acetals at its both ends. Into a 2-L flask made ofglass, 350 g of the resultant polyisobutyl vinyl ether having acetals atits both ends, 420 g of acetic acid, and 245 g of water were added, andstirred at 60° C. for 3 hours. The reaction mixture was neutralized witha saturated soda solution, and extracted with ethyl acetate. Then, ethylacetate was distilled off to obtain 310 g of polyisobutyl vinyl etherhaving formyl groups at its both ends. Into a 1-L autoclave made of SUS,130 g of the resultant polyisobutyl vinyl ether having formyl groups atits both ends, 420 g of ethanol, and 19.5 g of Raney nickel were added,and hydrogen (1961 kPa) was introduced. The autoclave was heated to 80°C., and stirring was carried out for 4 hours. After the reaction, Raneynickel was filtered off, and then the solvent was distilled off toobtain 111 g of Polyisobutyl vinyl ether (b) having hydroxyl groups atits both ends.

The molecular characteristics of the resultant Polyisobutyl vinyl ether(b) having hydroxyl groups at its both ends are shown in Table 2. Thenumber-average molecular weight and the molecular weight distributionwere measured under the same GPC measurement conditions as in ReferenceExample 1. TABLE 2 Polyisobutyl vinyl Number- Molecular ether havingHydroxyl Water average weight hydroxyl groups value content moleculardistribution at its both ends (mgKOH/g) (ppm) weight Mw/Mn (b) 58.2 752,250 1.23

EXAMPLE 1 Production of Polyurethane

Polyurethane 1 was produced from the ingredients shown in Table 3 by aone-shot method (preheating temperature: 120° C., reaction time: 6minutes, aging temperature: 80° C., aging time: 72 hours) usingPolyethyl vinyl ether (a) obtained Reference Example 1 as polyethylvinyl ether having hydroxyl groups at its both ends. TABLE 3 Polyvinylether 1,4- Poly- having hydroxyl groups Diphenylmethane Butanediolurethane at its both ends (g) diisocyanate (g) (g) 1 a: 72.2 19.3 3.5

The weight-average molecular weight of Polyurethane 1 is shown in Table5. The weight-average molecular weight was measured by means of GPC. TheGPC analysis conditions are the same as described above. Thepolyurethanes of the following examples were also measured for theirweight-average molecular weight under the same GPC conditions.

EXAMPLES 2 AND 3 Production of Polyurethanes

Polyurethanes 2 and 3 were synthesized in the same manner as in Example1, except that the ingredients for Polyurethanes 2 and 3 shown in Table4. TABLE 4 polyvinyl ether 1,4- Poly- having hydroxyl groupsDiphenylmethane Butanediol urethane at its both ends (g) diisocyanate(g) (g) 2 a: 86.9 49.7 13.4 3 b: 76.1 20.2 3.6

Each weight-average molecular weight of Polyurethanes 2 and 3 is shownin Table 5. TABLE 5 Weight-average Polyurethane molecular weight 139,700 2 50,200 3 51,300

COMPARATIVE EXAMPLE 1 Production of Polyurethane

Polyurethane 4 was produced from the ingredients in Table 6 in the samemanner as in Example 1 using polybutadiene polyol [manufactured byNIPPON SODA Co., Ltd, trade name: G-2000, hydroxyl value: 52.2 mgKOH/g,number-average molecular weight: 1900] as polybutadiene polyol. Thepolybutadiene polyol and 1,4-butanediol were not compatible with eachother at 120° C., resulting in a whitely turbid condition. TABLE 6Polybutadiene Diphenylmethane polyol diisocyanate 1,4-ButanediolPolyurethane (g) (g) (g) 4 110.4 52.1 14.1

The weight-average molecular weight of the resultant Polyurethane 4 isshown in Table 7. TABLE 7 Polyurethane Weight-average molecular weight 498,000

TEST EXAMPLE 1 Mechanical Strength, Transparency, and Solvent Solubility

By the use of the polyurethanes (Polyurethanes 1 to 4) produced inExamples 1 to 3 and Comparative Example 1, films with a thickness of 300micron were formed by press forming under the following conditions. Themechanical strength of each resultant film was measured in the followingmanner. Preheating conditions: Preheating was carried out in a mould at160° C. (Polyurethane 1), 180° C. (Polyurethane 2), 80° C. (Polyurethane3), or 180° C. (Polyurethane 4) for 5 minutes. Hot press conditions:Pressurization was carried out at 160° c. (Polyurethane 1), 180° C.(Polyurethane 2), 80° C. (Polyurethane 3), or 180° C. (Polyurethane 4)at 14710 kPa, for 120 seconds, and at 2942 kPa for 30 seconds, andsubsequently, pressurization was carried out at 20° C. at 6864 kPa for120 seconds.

A tensile test was carried out at 23° C. according to JIS K-7311 foreach aforesaid polyurethane film.

The measurement results thereof, the outward appearances of the films,and the solubilities in THF (tetrahydrofuran) are shown in Table 8.TABLE 8 Tensile 100% Tensile strength Elongation THF Hardness Modulusstrength at break at break polyurethane (JIS A) (MPa) (MPa) (MPa) (%)Transparency Solubility 1 65 1.6 2.9 1.4 1500 ◯ ◯ 2 84 8.3 9.5 9.3 230 Δto ◯ ◯ 3 66 1.7 2.7 1600 Δ to ◯ ◯ 4 52 0.9 1.1 0.7 460 X X

Meanings of the evaluations as to the transparency and the THFsolubility (0.2 g of the sample was dissolved in 99.8 g of THF) in Table8 were as follows.

Transparency: ◯ Transparent, Δ A little turbid, X Not transparent THFsolubility: ◯ No insoluble matter observed, X Insoluble matter observed.

Polyurethane 1 to 3 of the present invention each showed excellenttensile strength at break, transparency, and solvent solubility ascompared with Polyurethane 4.

EXAMPLE 4 Production of Urethane Acrylate

Into a 1-L flask made of glass, 358.4 g of diethylene glycol monoethylether acetate, 383 g (0.2 mol) of Polyethyl vinyl ether a havinghydroxyl groups at its both ends obtained in Reference Example 1 and104.8 g (0.4 mol) of 4,4′-diisocyanate dicyclohexylmethane were charged.The mixture was heated up to 70° C. with stirring under a nitrogen flowatmosphere, and the reaction was continued for 2 hours with thetemperature kept at 70° C. The reaction mixture was once cooled down toroom temperature, and 46.4 g (0.4 mol) of 2-hydroxyethylacrylate wasadded thereto. The mixture was heated to 80° C., and allowed to reactfor 2 hours. The IR spectrum of the reaction product was measured. As aresult, the absorption of an isocyanate group was not detected. Thesolid content of the reaction product was 59 wt %.

EXAMPLE 5 Production of Polyurethane

Polyurethane 5 was produced from the ingredients shown in Table 9 in thesame manner as in Example 1. As the polyoxypropylene glycol,polyoxypropylene glycol [manufactured by SANYO CHEMICAL INDUSTRIES,Ltd., trade name: PP-2000, hydroxyl value: 55.5 mgKOH/g, number-averagemolecular weight: 2000] was used, and as Polyethyl vinyl ether havinghydroxyl groups at its both ends, polyethylvinyl ether (a) obtained inReference Example 1 was used. TABLE 9 Polyvinyl ether Polyoxy- havinghydroxyl 1,4- Poly- propylene groups at its Diphenylmethane Butanediolurethane glycol (g) both ends (g) diisocyanate (g) (g) 5 66.4 a: 28.549.7 13.4

The weight-average molecular weight of the resultant Polyurethane 5 isshown in Table 10. TABLE 10 Polyurethane Weight-average molecular weight5 128,000

COMPARATIVE EXAMPLE 2 Production of Polyurethane

Polyurethane 6 was produced from the ingredients shown in Table 11 inthe same manner as in Example 1 using by polyoxypropylene glycol[manufactured by SANYO CHEMICAL. INDUSTRIES, Ltd., trade name: PP-2000,hydroxyl value: 55.5 mgKOH/g, number-average molecular weight: 2000] aspolyoxypropylene glycol. TABLE 11 Poly- Polyoxypropylene Diphenylmethane1,4- urethane glycol (g) diisocyanate (g) Butanediol (g) 6 122.5 61.016.5

The weight-average molecular weight of the resultant Polyurethane 6 isshown in Table 12. TABLE 12 polyurethane Weight-average molecular weight6 121,000

COMPARATIVE EXAMPLE 3 Production of Polyurethane

Polyurethane 7 was produced from the ingredients shown in Table 13 inthe same manner as in Example 1 using polyester polyol comprising 1,4-butanediol and adipic acid [manufactured by ASAHI DENKA Co., Ltd.,trade name: F9-30, Hydroxyl value: 55.3 mgKOH/g, number-averagemolecular weight: 2000] as the polyester polyol. TABLE 13 Poly-Polyester Diphenylmethane 1,4-butanediol urethane polyol (g)diisocyanate (g) (g) 7 122.8 60.5 16.7

The weight-average molecular weight of the resultant Polyurethane 7 isshown in Table 14. TABLE 14 Polyurethane Weight-average molecular weight7 93,000

TEST EXAMPLE 2 Water Resistance

The water resistances of Polyurethanes 1 to 3, and 5 to 7 obtained inthe foregoing manner were evaluated in the following manner.

Each polyurethane film obtained in the same manner as in Test Example 1was dipped in 100° C. water, and the changes with the elaspe of time inretention of the weight-average molecular weight were measured. Theweight-average molecular weight was measured in the same manner as inExample 1. The measurement results are shown in Table 15. TABLE 15 Poly-Weight-average molecular weight retention (%) urethane After 7 daysAfter 14 days 1 86 82 2 79 82 3 90 85 5 75 60 6 34 26 7 23 7

Polyurethanes 1 to 3, and 5 of the present invention showed excellentwater resistances as compared with Polyurethanes 6 and 7.

TEST EXAMPLE 3 Thermal Aging Resistance

The thermal aging resistances of Polyurethanes 1 to 3, and 5 and 6,obtained in the foregoing manner were evaluated in the following manner.

Each polyurethane film obtained in the same manner as in Test Example 1was placed in a 125° C. oven, and the changes with elaspe of time inretention of the weight-average molecular weight were measured. Theweight-average molecular weight was measured in the same manner as withExample 1. The measurement results are shown in Table 16. TABLE 16Weight-average molecular weight Polyurethane retention (%) after 7 days1 108 2 103 3 111 5 108 6 67

Polyurethanes 1 to 3, and 5 of the present invention showed excellentthermal aging resistances as compared with Polyurethane 6.

TEST EXAMPLE 4 Electric Characteristics

The electric characteristics of Polyurethanes 2, 3, 6, and 7 obtained inthe foregoing manner were evaluated in the following manner.

Each polyurethane film obtained in the same manner as in Test Example 1was measured for the volume resistivity according to JIS K6911. Themeasurement results are shown in Table 17. TABLE 17 Volume resistivityPolyurethane (Ωcm) 2 3.7 × 10¹⁵ 3 8.1 × 10¹⁵ 6 1.0 × 10¹³ 7 4.9 × 10¹⁴

Polyurethanes 2 and 3 of the present invention showed excellentelectrical insulation properties as compared with Polyurethanes 6 and 7.

EXAMPLE 6 Production of Aqueous Polyurethane Resin

Into a 1-L flask made of glass, 153g (0.08mol) of Polyethyl vinyl ether(a) having hyroxyl groups at its both ends obtained in Reference Example1 and 16.9 g (0.11 mol) of dimethylol butanoic acid (DMBA) were charged,and heated to 80° C. with stirring under a nitrogen atmosphere. Whilesupplying nitrogen into the flask, and simultaneously carrying outevacuation using a vacuum pump, stirring was further continued for 30minutes. After stopping the evacuation by the vacuum pump, thetemperature in the flask was cooled to 60° C., and 60 g of acetone wasadded thereto. After increasing the temperature to 80° C. again, 117.8 g(0.53 mol) of isophorone diisocyanate (IPDI) was added dropwise over 1hour. After the completion of dropwise addition, stirring was continuedwith the temperature in the flask kept at 80° C. until the reaction rateof isocyanate groups in the reaction solution became 95% or more.Thereafter, the reaction product was cooled down to 60° C., and 11.6 g(0.11 mol) of triethylamine was added thereto to neutralize the carboxylgroup in the urethane prepolymer, thereby obtain a urethane prepolymer.

To the resulting urethane prepolymer, 480 g of distilled water was addedgradually with stirring by a homomixer at 3000 to 4000 rpm to obtain anaqueous dispersion of an urethane prepolymer. While continuing thestirring by the homomixer, 19.9 g (0.33 mol) of ethylenediamine (EDA)was added to the aqueous dispersion to obtain an objective Aqueouspolyurethane resin 1.

EXAMPLE 7 Production of Aqueous Polyurethane Resin

Aqueous polyurethane resin 2 was obtained in the same manner in withExample 6, except that 180 g (0.08 mol) of, Polyisobutyl vinyl ether (b)having hydroxyl groups at its both ends obtained in Reference Example 2was used in place of Polyethyl vinyl ether (a) having hydroxyl groups atits both ends obtained in Reference Example 1.

COMPARATIVE EXAMPLE 4 Production of Aqueous Polyurethane Resin

Aqueous polyurethane resin 3 was obtained in the same manner as inExample 6, except that 161 g (0.08 mol) of polyoxypropylene glycol[manufactured by SANYO CHEMICAL INDUSTRIES, Ltd., trade name: PP-2000,hydroxyl value: 55.5 mgKOH/g, number-average molecular weight: 2000] wasused in place of Polyethyl vinyl ether (a) having hydroxyl groups at itsboth ends obtained in Reference Example 1.

COMPARATIVE EXAMPLE 5 Production of Aqueous Polyurethane Resin

Aqueous polyurethane resin 4 was obtained in the same manner as inExample 6, except that 162 g (0.08 mol) of polyester polyol comprising1,4-butanediol and adipic acid [manufactured by ASAHI DENKA Co., Ltd.,trade name: F9-30, hydroxyl value: 55.3 mgKOH/g, number-averagemolecular weight: 2000] was used in place of Polyethyl vinyl ether (a)having hydroxyl groups at its both ends obtained in Reference Example 1.

TEST EXAMPLE 5 Water Resistance

The water resistance of each film obtainable from Aqueous polyurethaneresins 1 to 4 obtained in the foregoing manner was evaluated in thefollowing manner.

Each polyurethane film obtained in the same manner as in Test Example 1was dipped in 100° C. water for 7 days, and the weight-average molecularweight was measured. The retention of the weight-average molecularweight (weight-average molecular weight after test/before test×100) wasdetermined from the measurement result. The results of the retention areshown in Table 18. TABLE 18 Aqueous Weight-average molecularpolyurethane resin weight retention (%) 1 75 2 86 3 31 4 18

Aqueous polyurathane resins 1 and 2 of the present invention showedexcellent water resistances as compared with Aqueous polyurethane resins3 and 4.

EXAMPLE 8 Production of Urethane Acrylate

A urathane acrylate was obtained in the same manner as in Example 4,except that 450 g (0.2 mol) of Polyisobutyl vinyl ether (b) havinghydroxyl groups at its both ends obtained in Reference Example 2 wasused in place of Polyethyl vinyl ether (a) having hydroxyl groups at itsboth ends obtained in Reference Example 1.

COMPARATIVE EXAMPLE 6 Production of Urethane Acrylate

A urethane acrylate was obtained in the same manner as in Example 4,except 404 g (0.2 mol) of polyoxypropylene glycol [manufactured by SANYOCHEMICAL INDUSTRIES, Ltd., trade name: PP-2000, hydroxyl value: 55.5mgKOH/g, number-average molecular weight:2000]was used in place ofPolyethyl vinyl ether (a) having hydroxyl groups at its both endsobtained in Reference Example 1.

COMPARATIVE EXAMPLE 7 Production of Urethane Acrylate

A urethane acrylate was obtained in the same manner as in Example 4,except that 406 g (0.2 mol) of polyester polyol comprising1,4-butanediol and adipic acid [manufactured by ASAHI DENKA Co., Ltd.,trade name: F9-30, hydroxyl value: 55.3 mgKOH/g, number-averagemolecular weight: 2000] was used in place of Polyethyl vinyl ether (a)having hydroxyl groups at its both ends obtained in Reference Example 1.

TEST EXAMPLE 6 Mechanical Strength, Water Resistance, and Adhesion

Into each 60 wt % THF solution of the urethane acrylates obtained inExamples 4 and 8, and Comparative Examples 6 and 7, 2.0 parts by weightof IRGACURE184 (manufactured by Ciba Speciality Chemicals), 0.5 parts byweight of IRGACURE 819 (manufactured by Ciba Speciality Chemicals), and0.3 parts by weight of IRGANOX 1035 (manufactured by Ciba SpecialityChemicals) were dissolved per 100 parts by weight of the urethaneacrylate. Subsequently, the resulting mixture was applied onto a glasspanel by means of a 0.27-mm applicator. The coated panel was subjectedto vacuum drying overnight in a 60° C. oven, and then dried overnight at23° C./humidity 50%. Thereafter, curing was carried out under thefollowing conditions: Curing apparatus: UV curing apparatus manufacturedby EYE GRAPHICS Co., Ltd.

Lamp: Metal halide lamp (optical path length 25 cm) and high pressuremercury lamp (optical path length 25 cm)

Intensity: 80 W/cm

Conveyor speed: 4.6 m/min

Irradiation distance: 50 cm

The mechanical strength and the water resistance of the resulting curedfilm were evaluated. The mechanical strength was evaluated by a tensiletest, and the water resistance was evaluated based on the changes withthe elapse of time in retention of the Tensile strength (Tensilestrength after test/before test×100) in the tensile test, during whichthe cured film was dipped in 100° C. water for 7 days or 14 days. Thetensile test was carried out according to JIS K-7113.

The 60 wt % THF solution of the urethane acrylate obtained in Example 4was applied onto standard test panels ABS (acrylonitrile butadienestyrene), PS (polystyrene), and PC (polycarbonate) manufactured byNippon. Test panel Osaka Co., Ltd., and dried and cured under the sameconditions as described above. The adhesion of each resulting film wasevaluated using the following test method.

Adhesion testing method: the cross-cut tape method defined according toJIS K5400 was carried out. Cuts in a grid were incised at an interval of1 mm through the film, and then the film was peeled off with acellophane tape. The results are referred to in terms of the number ofsquares remaining without having been peeled off out of 100 squares asthe evaluation score.

The foregoing measurement results are shown in Tables 19 and 19-2. TABLE19 Urethane Tension modulus Retention of tensile strength (%) acrylate(MPa) After 7 days After 14 days Example 4 2.3 86 83 Example 8 2.0 90 87Comparative 4.6 45 38 Example 6 Comparative 5.1 36 20 Example 7

TABLE 19-2 Standard test panel Adhesion ABS 93/100 PS 98/100 PC 97/100

Each cured product obtainable by curing the urethane acrylates obtainedin Examples 4 and 8 showed excellent mechanical strength and water,resistance as compared with the cured products obtainable by curing theurethane acrylates obtained in Comparative Examples 6 and 7.

The cured product obtainable by curing the urethane acrylate obtained inExample 4 showed excellent adhesion to the ABS, PS, and PC standard testpanels.

EXAMPLE 9 Production of Urethane Alkenyl Ether

Into a 500-mL flask made of glass, 43.0 g (0.25 mol) of 2,4-tolylenediisocyanate, 287.3 g (0.15 mol) of the polyethyl vinyl ether (a) havinghydroxyl groups at its both ends obtained in Reference Example 1 and0.23 g (0.36 mol) of di-n-butyltin dilaurate were charged. The mixturewas heated up to 80° C. with stirring under a nitrogen flow atmosphere,and allowed to react for 1 hour. The reaction mixture was once cooleddown to 60° C., and 18.5 g (0.2 mol) of 2-hydroxyethyl vinyl ether wasadded thereto. The mixture was allowed to react at 70° C. for one hour.The IR spectrum of the reaction product was measured. As a result, theabsorption of an isocyanate group was not detected.

EXAMPLE 10 Production of Urethane Alkenyl Ether

An urethane alkenyl ether was obtained in the same manner as in Example9, except that 337.5 g (0.15 mol) of Polyisobutyl vinyl ether (b) havinghydroxyl groups at its both ends obtained in Reference Example 2 wasused in place of Polyethyl vinyl ether (a) having hydroxyl groups at itsboth ends obtained in Reference Example 1.

COMPARATIVE EXAMPLE 8 Production of Urethane Alkenyl Ether

An urethane alkenyl ether was obtained in the same manner as in Example9, except that 303 g (0.15 mol) of polyoxypropylene glycol [manufacturedby SANYO CHEMICAL INDUSTRIES, Ltd., trade name: PP-2000, hydroxyl value:55.5 mgKOH/g, number-average molecular weight: 2000] was used in placeof Polyethyl vinyl ether (a) having hydroxyl groups at its both endsobtained in Reference Example 1.

TEST EXAMPLE 7 Mechanical Strength, Water Resistance, and the Like

Each urethane alkenyl ether obtained in Examples 9 and 10, andComparative Example 8 was cured under the following conditions, and themechanical strength of the resultant film was measured.

A THF solution (solid content 60%) of the urethane alkenyl ether wasprepared, to which 2.5 parts by weight of OPTOMER SP-170 (manufacturedby ASAHI DENKA Co., Ltd.) was dissolved per 100 parts by weight of theurethane alkenyl ether. Then, the solution was applied onto a glasspanel by means of a 0.254-mm applicator. The coated panel was subjectedto vacuum drying overnight in a 60° C. oven, and irradiated with anultraviolet ray until the film was cured under the following conditions.Curing apparatus: UV curing apparatus manufactured by EYE GRAPHICS Co.,Ltd.

Lamp: Metal halide lamp (optical path length 25 cm) and high pressuremercury lamp (optical path length 25 cm)

Intensity: 160 W/cm

Conveyor speed: 4.6 m/min

Irradiation distance: 20 cm

Each resultant 50-m cured film was subjected to a tensile test at 23° C.according to JIS K-7113. The resultant cured film was held for 7 daysand for 14 days in a 90° C./humidity 95% constant-temperatureconstant-humidity vessel. Then, the changes with the elapse of time inretention of Tensile strength were measured to evaluate the moist heatresistance (weather resistance and water resistance).

The foregoing measurement results are shown in Tables 20 and 20-2. TABLE20 Tensile 100% Tensile strength Elongation Tension Urethane Modulusstrength at break at break modulus alkenyl ether (MPa) (MPa) (MPa) (%)(MPa) Example 9 1.1 1.9 1.9 110 2.0 Example 10 1.1 1.8 1.8 120 1.9Comparative 2.3 2.9 2.9 170 3.4 Example 8

TABLE 20-2 Retention of tensile strength (%) Urethane alkenyl etherAfter 7 days After 14 days Example 9 93 90 Example 10 95 89 ComparativeExample 8 52 45

Each cured product obtainable by curing the urethane acrylates obtainedin Examples 9 and 10 was low in modulus of elasticity and flexible, andin addition, showed excellent moist heat resistance (weather resistanceand water resistance) as compared with the cured product obtainable bycuring the urethane alkenyl ether obtained in Comparative Example 8.

EXAMPLE 11 Curing of Composition having Urethane Alkenyl Ether and aCompound having a Maleimido Group

The urethane alkenyl ether obtained in Example 9 and 4,4′-bismaleimidediphenylmethane were mixed so that the ratio of the number of moles ofthe maleimido group to the number of moles of the urethane alkenyl etherbecame 1.0. Then, 2.0 parts by weight of IRGACURE 184 (manufactured byCiba Speciality Chemicals) and 0.5 parts by weight of IRGACURE 819(manufactured by Ciba Speciality Chemicals) were added per 100 parts byweight of the mixture. Then, THF was added thereto to prepare a 40 wt %solution. The resulting mixture was applied onto a glass panel by meansof a 0.254-mm applicator. The coated panel was subjected to vacuumdrying in a 60° C. oven overnight, and then irradiated with anultraviolet ray under the same conditions as in Test Example 7,resulting in a cured coating.

COMPARATIVE EXAMPLE 9 Curing of Composition having Urethane AlkenylEther and a Compound having a Maleimido Group

A cured coating was obtained in the same manner as in Example 11, exceptthat the urethane alkenyl ether obtained in Comparative Example 8 wasused in place of the urethane alkenyl ether obtained in Example 9.

TEST EXAMPLE 8 Water Resistance

The water resistance was evaluated by the use of each cured coatingobtained in, Example 11 and Comparative Example 9. The water resistancetest was carried out in the same manner as with Test Example 7.

The measurement results are shown in Table 21. TABLE 21 Retention oftensile strength (%) Cured coating After 7 days After 14 days Example 1197 93 Comparative Example 9 68 57

The cured coating obtained in Example 11 showed excellent waterresistance as compared with the cured coating obtained in ComparativeExample 9.

EXAMPLE 12 Production of Polyurethane (Coating)

Into a glass bottle, 10.04 g of ACRYDICA-801 (solid content 50% , whichalso be abbreviated hereinafter as A-801, manufactured by Dainippon Ink& Chemicals, Inc.) as is an acryl polyol, 0.255 g of Polyethyl vinylether (a) having hydroxyl groups at its both ends obtained in ReferenceExample 1 (which also be abbreviated hereinafter as (a), 0.855 g ofSUMIDURN-3300 (which also be abbreviated hereinafter asN-3300,manufactured by Sumika Bayer Urethane Co., Ltd.) which is theisocyanurate form of hexamethylene diisocyanate, 6.35 g of xylene (whichbe abbreviated hereinafter as XY), and 0.002 g of dibutyltin dilaurate(which also be abbreviated hereinafter as DBTDL) were charged, andstirred at room temperature for 2 minutes. The acryl urethane paint thusproduced was applied onto a zinc phosphated steel panel by means of anapplicator. The panel was allowed to stand for 10 minutes, and then,dried at 80° C. for 20 minutes, and allowed to stand overnight at 23°C./humidity 50%. As a result, a polyurethane (coating) with a thicknessof about 20 μm was obtained.

EXAMPLE 13 Production of Polyurethane (Coating)

A polyurethane (coating) was obtained by the same operation as inExample 12, except that the raw material composition was changed to thatshown in Table 22.

COMPARATIVE EXAMPLES 10 TO 12 Production of Polyurethane (Coating)

Each polyurethane (coating) was obtained by the same operation as inExample 12, except that the raw material composition was changed to thatshown in Table 22. PTG2000 in Table 22 means polytetramethylene etherglycol (number-average molecular weight =2000).

TEST EXAMPLE 9 Solvent Resistance, Impact Resistance, Pencil Hardness,and Adhesion

Each polyurethane (coating) obtained in Examples 12 and 13, andComparative Examples 10 to 12 were tested for the solvent resistance,the impact resistance, the pencil hardness, and the adhesion. Theadhesion, the pencil hardness, the impact resistance, and the solventresistance were evaluated in the following manner.

Adhesion: the test was carried out in the same manner as in the adhesiontesting method described in Test. Example 6. Pencil hardness: the pencilscratch test defined in JIS K5400 was carried out, so that theevaluation of the coating according to the scratch was carried out. Theresults are referred to as the highest hardness of a pencil which willnot give scratches thereon even when it scratches the coating.

Impact resistance: the Dupont type impact resistance test (½ inch)defined in JIS K5400 was carried out, so that the evaluation of thecoating according to the crack and the peeling was carried out. A 1000-gweight was used. The results are referred to as the maximum drop heightof the weight which will not cause cracks or peeling even when it givesan impact thereon.

Solvent resistance: the coating was rubbed under a load of 500 g with agauze dipped in methyl ethyl ketone (MEK) (rubbing was carried out). Theresults are referred to as the ranks ({circle over (◯)}: 100 times ormore, ◯: 50 time or more and less than 100 times, X: less than 50 times)according to the number of reciprocating rubbing cycles until the steelpanel surface is exposed.

The foregoing test results are shown in Table 22. TABLE 22 ImpactPolyurethane Raw material composition (g) Solvent resistance Pencil(Coating) A-801 a PTG2000 N-3300 DBTDL XY resistance (cm) hardnessAdhesion Example 12 10.04 0.255 0.857 0.0018 6.34 ⊚ 30 F 100/100 Example13 10.02 0.507 0.852 0.0020 6.81 ⊚ 45 F 100/100 Comparative 10.01 0.2520.862 0.0021 6.36 ⊚ 25 F 100/100 Example 10 Comparative 10.01 0.5040.865 0.0017 6.83 ⊚ 35 HB 100/100 Example 11 Comparative 10.04 0.8570.0021 5.89 ⊚ 15 F 100/100 Example 12

Although each polyurethane (coating) obtained in Examples 12 and 13 ofthe present invention was equal in solvent resistance, pencil hardness,and adhesion to that not having Polyethyl vinyl ether a having hydroxylgroups at its both ends obtained in Reference Example 1, it showedexcellent impact resistance.

EXAMPLE 14 Production of Polyurethane (Coating)

Into a glass bottle, 10.0 g of Polyethyl vinyl ether (a) having hydroxylgroups at its both ends obtained in Reference Example 1 (which also beabbreviated hereinafter as (a), 2.54 g of SUMIDUR N-3300 (which also beabbreviated hereinafter as N-3300, manufactured by Sumika Bayer UrethaneCo., Ltd.) which is the isocyanurate form of hexamethylene diisocyanate,23.3 g of xylene (which also be abbreviated hereinafter as XY), and0.003 g of dibutyltin dilaurate (which also be abbreviated hereinafteras DBTDL) were charged, and stirred at room temperature for 2 minutes.The acryl urethane paint thus produced was applied onto the standardtest panels PS (polystyrene), aluminum, and glass panels manufactured byNippon Test panel Osaka Co., Ltd., with an applicator. Each panel wasallowed to stand for 10 minutes, and then, dried at 80° C. for 20minutes, and allowed to stand overnight at 23° C./humidity 50%. As aresult, a polyurethane (coating) with a thickness of about 20 μm wasobtained.

EXAMPLE 15 Production of Polyurethane (Coating)

A polyurethane (coating) was obtained by the same operation as inExample 14, except that the raw material composition was changed to thatshown in Table 23. In Table 23, PTG2000 means polytetramethylene etherglycol [manufactured by HODOGAYA CHEMICAL Co., Ltd., trade name:PTG-2000SN, hydroxyl value: 56.3 mgKOH/g, number-average molecularweight: 2000], and G2000 means polybutadiene polyol [manufactured byNIPPON SODA Co., Ltd., trade name: G-2000, hydroxyl value: 52.2 mgKOH/g,number-average molecular weight: 1900].

COMPARATIVE EXAMPLES 13 TO 16 Production of Polyurethane (Coating)

A polyurethane (coating) was obtained by the same operation as inExample 14, except that the raw material composition was changed to thatshown in Table 23. In Table 23, A-801 means ACRYDIC A801 which is anacryl polyol (solid content 50%, which also be hereinafter abbreviatedas A-801, manufactured by Dainippon Ink & Chemicals, Inc., hydroxylvalue 50.0 mgKOH/g, number-average molecular weight: 2200), and F9-30maens polyester polyol comprising 1,4-butanediol and adipic acid[manufactured by ASAHI DENKA Co., Ltd., trade name: F9-30, Hydroxylvalue: 55.3 mgKOH/g, number-average molecular weight: 2000].

TEST EXAMPLE 10 Adhesion

An adhesion test was carried out by the use of each polyurethane(coating) obtained in Examples 14 and 15, and Comparative Examples 13 to16. The adhesion test was carried out in the same manner as with theadhesion testing method described in Test Example 6. As base materials,standard test panels PS (polystyrene) and aluminum manufactured byNippon Test panel Osaka Co., Ltd., were used.

The foregoing test results are shown in Table 23-2. TABLE 23 Rawmaterial composition (g) Polyurethane (Coating) a PTG2000 G2000 A-801F9-30 N-3300 DBTDL XY Example 14 10.0 2.54 0.003 23.3 Example 15 3.0 7.02.01 0.003 22.3 Comparative Example 13 10.0 1.93 0.003 22.2 ComparativeExample 14 10.0 1.79 0.003 21.9 Comparative Example 15 20.0 1.71 0.00311.7 Comparative Example 16 10.0 1.89 0.003 22.1

TABLE 23-2 Adhesion polyurethane (Coating) Polystyrene Aluminum Example14 100/100 100/100 Example 15 100/100 100/100 Comparative Example 13100/100  0/100 Comparative Example 14  98/100  37/100 ComparativeExample 15  7/100 100/100 Comparative Example 16  0/100  13/100

Each polyurethane (coating) obtained in Examples 14 and 15 of thepresent invention showed excellent adhesion as compared with thepolyurethane (coatings) obtained in Comparative Examples 13 to 16.

EXAMPLE 16 Production of Polyurethane (Urethane Resin for Ink)

Into a 200-mL flask made of glass, 72.9 g (0.04 mol) of Polyethyl vinylether (a) having hydroxyl groups at-its both ends obtained in ReferenceExample 1, 1.7 g (0.02 mol) of 1,4-butanediol and 22.3 g (0.1 mol) ofisophorone diisocyanate were charged, and the mixture was heated to 100°C. with stirring under a nitrogen atmosphere, and allowed to react for 9hours. Then, 40 mL of toluene and 40 mL of methyl ethyl ketone wereadded thereto, and the mixture was cooled down to room temperature toobtain an urethane prepolymer. Into a 500-mL flask made of glass, 52 mLof toluene, 52 mL of methyl ethyl ketone, 96 mL of 2-propanol, 8.5 g(0.05 mol) of isophoronediamine, and 0.65 g (0.005 mol) of dibutylaminewere charged, and the resultant urethane prepolymer obtained above wasadded thereto with stirring at room temperature. This solution washeated to 50° C., and allowed to react for 4 hours to obtain anobjective polyurethane. The resultant polyurethane had a weight-averagemolecular weight of 9,000, and a solid content of 32 wt %.

COMPARATIVE EXAMPLE 17 Production of Polyurethane (Urethane Resin forInk)

A polyurethane was obtained in the same manner as in Example 16, exceptthat 77.6 g (0.04 mol) of poly(3-methyl-1,5-pentane adipate)diol[KURAPOL 2010, manufactured by Kuraray, Co., Ltd., hydroxyl value: 57.8mgKOH/g, number-average molecular weight: 1940) was used in place ofPolyethyl vinyl ether (a) having hydroxyl groups at its both endsobtained in Reference Example 1. The resulting polyurethane had aweight-average molecular weight of 13,000 and a solid content of 34 wt%.

TEST EXAMPLE 11 Adhesion

Each polyurethane obtained in Example 16, and Comparative Example 17 wasapplied onto standard test panels PS (polystyrene), FRP (glass fiberreinforced plastic), aluminum, zinc phosphated steel panel,PP[polypropylene, corona discharge treatment, wetting index: 40 mN/m(JIS K6768)], and glass with an applicator. The coated panels were driedat 80° C. for 30 minutes to thereby obtain coatings each having athickness of about 30 μm. A test of adhesion was carried out using eachresulting coating in the same manner as in Test Example 6. The testresults are shown in Table 24. TABLE 24 Adhesion Comparative Standardtest panel Example 16 Example 17 PS 100/100 45/100 FRP  95/100 25/100Aluminum 100/100 72/100 Zinc phosphated steel panel 100/100 26/100 PP100/100 21/100 Glass 100/100 85/100

The coating obtained from the polyurethane obtained in Example 16 showedexcellent adhesion as compared with the polyurethane obtained inComparative Example 17.

EXAMPLE 17 Production of Ester Acrylate

Into a 300-mL flask made of glass equipped with a Dean-Stark trap, 99.5g (0.05 mol) of Polyethyl vinyl ether (a) having hydroxyl groups at itsboth ends obtained in Reference Example 1, 50 g of toluene, 0.6 g (0.005mol) of hydroquinone, and 0.6 g (0.003 mol) of p-toluenesulfonicacid-hydrate were charged, and the mixture was heated to 100° C. Then,24.1 g (0.3 mol) of acrylic acid was added dropwise over 20 minutes, andthe mixture was allowed to react for 15 hours under ref lux whiledistilling away the resulting water. After cooling the reaction mixture,an organic layer to which 210 g of toluene had been added was washed 3times with a 5 wt % sodium hydroxide aqueous solution and 165 g ofwater. To the organic layer, 0.6 g of p-methoxyphenol was added, andconcentrated for 30 minutes under the conditions of 50° C. and 4.1 kPa.As a result, a viscous liquid was obtained. The ¹H-NMR of the resultantviscous liquid was measured. As a result, the peak derived from thehydroxyl group disappeared, and the peak derived from the acryl groupwas observed.

COMPARATIVE EXAMPLE 18 Production of Ester Acrylate

An ester acrylate was obtained in the same manner as in Example 17,except that 110 g (0.05 mol) of polyoxypropylene glycol [manufactured bySANYO CHEMICAL INDUSTRIES, Ltd., trade name: PP-2000, hydroxyl value:55.5 mgKOH/g, number-average molecular weight: 2000] was used in placeof Polyethyl vinyl ether (a) having hydroxyl groups at its both endsobtained in Reference Example 1.

TEST EXAMPLE 12 Water Resistance

The water resistance was evaluated by the use of a cured coatingobtained by curing each ester acrylate obtained in Example 17 andComparative Example 18 in the same manner as in Test Example 6. Thewater resistance test was carried out in the same manner as in TestExample 6.

The measurement results are shown in Table 25. TABLE 25 Retention oftensile strength (%) Ester acrylate After 7 days After 14 days Example17 85 80 Comparative Example 18 55 42

The cured product obtainable by curing the ester acrylate obtained inExample 17 showed excellent water resistance as compared with the curedproduct obtainable by curing the ester acrylate obtained in ComparativeExample 18.

EXAMPLE 18 Production of Alkenyl Ether

Into a 1-L flask made of glass and equipped with a condenser tube, 400 g(0.22 mol) of Polyethyl vinyl ether (a) having hydroxyl groups at itsboth ends obtained in Reference Example 1, 160 g (2.2 mol) of ethylvinyl ether, and 2.7 g (0.007 mol) of diaceto (1,10-phenanthroline)palladium were charged, and allowed to react at 30° C. for 24 hours. Thereaction mixture was concentrated under reduced pressure to therebydistill away excess ethyl vinyl ether, and in a viscous liquid wasobtained. The ¹H-NMR of the resultant viscous liquid was measured. As aresult, the peak derived from the hydroxyl group disappeared, and thepeak derived from the alkenyl ether group was observed.

COMPARATIVE EXAMPLE 19 Production of Alkenyl Ether

An alkenyl ether was obtained in the same manner as in Example 18,except that 450 g (0.22 mol) of polyoxypropylene glycol [manufactured bySANYO CHEMICAL INDUSTRIES, Ltd., trade name: PP-2000, hydroxyl value:55.5 mgKOH/g, number-average molecular weight: 2000] was used in placeof Polyethyl vinyl ether (a) having hydroxyl groups at its both endsobtained in Reference Example 1.

TEST EXAMPLE 13 Thermal Aging Resistance

Each alkenyl ether obtained in Example 18 and Comparative Example 19 wascured in the same manner as in Test Example 7. The thermal agingresistance was evaluated by the use of each resultant cured coating. Thethermal aging resistance was evaluated by placing each resultant curedcoating in a 125° C. oven, and according to the changes the elpase ofwith time in retention of the Tensile strength in a tensile test. Thetensile test was carried out in the same manner as in Test Example 6.

The measurement results are shown in Table 26. TABLE 26 Retention oftensile strength (%) Alkenyl ether After 7 days Example 18 103Comparative Example 19 70

The cured product obtainable by curing the alkenyl ether obtained inExample 18 showed excellent thermal aging resistance as compared withthe cured product obtainable by curing the alkenyl ether obtained inComparative Example 19.

EXAMPLE 19 Curing of Composition having an Alkenyl Ether and a Compoundhaving a Maleimido Group

The alkenyl ether obtained in Example 18 and 4,4′-bismaleimidediphenylmethane were mixed so that the ratio of the number of moles ofthe compound having a maleimido group to the number of moles of thealkenyl ether became 1.0. 2.0 parts by weight of IRGACURE 184(manufactured by Ciba Speciality Chemicals) and 0.5 part by weight ofIRGACURE 819 (manufactured by Ciba Speciality Chemicals) were added per100 parts by weight of the mixture. Then, THF was added thereto toprepare a 40 wt % solution. The solution was applied onto a glass panelwith a 0.254-mm applicator. The coated panel was subjected to vacuumdrying in a 60° C. oven overnight, and then irradiated with anultraviolet ray under the same conditions as with Test Example 7,resulting in a cured coating.

COMPARATIVE EXAMPLE 20 Curing of Composition having an Alkenyl Ether anda Compound having a Maleimido Group

A cured coating was obtained in the same manner as in Example 19, exceptthat the urethane alkenyl ether obtained in Comparative Example 19 wasused in place of the urethane alkenyl ether obtained Example 18.

TEST EXAMPLE 14 Thermal Aging Resistance

The thermal aging resistance was evaluated by the use of each curedcoating obtained in Example 19 and Comparative Example 20. Theevaluation of the thermal aging resistance was carried out according tothe method described in Test Example 13.

The measurement results are shown in Table 27. TABLE 27 Retention oftensile strength (%) Composition After 7 days Example 19 104 ComparativeExample 20 66

The cured coating obtained in Example 19 showed excellent thermal agingresistance as compared with the cured coating obtained in ComparativeExample 20.

INDUSTRIAL AVAILABILITY

The present invention provides a polyurethane, a polyester, and thelike, excellent in flexibility, compatibility with a low polarity resin,uniformity of composition, mechanical strength, solubility, stickiness,bonding property, adhesion, electrical insulation property, weatherresistance, water resistance, transparency, thermal aging resistance,results in a pressure cooker test, or the like.

1. A polyurethane having a structural unit represented by formula (XXX):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl, R², R³ and R⁴, independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or substituted orunsubstituted aralkyl, and R¹s, R²s, R³s, and R⁴s, when they are eachpresent two or more in number, may be the same or different.
 2. Apolyurethane having a structural unit represented by formula (I):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkylsubstituted or unsubstituted aryl or substituted or unsubstitutedaralkyl, R², R³ and R⁴ independently represent a hydrogen atom,substituted or unsubstituted lower alkyl substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or substituted orunsubstituted aralkyl R¹s, R²s, R³s and R⁴s, when they are each presenttwo or more in number, may be the same or different, and R⁵ represents ahydrogen atom, substituted or unsubstituted lower alkyl, substituted orunsubstituted cycloalkyl, substituted or unsubstituted aryl, orsubstituted or unsubstituted aralkyl.
 3. The polyurethane according toclaim 1 or 2, wherein the weight-average molecular weight thereof is30000 to
 1000000. 4. The polyurethane according to claim 1, which is aurethane acrylate.
 5. An urethane acrylate having a structural unitrepresented by formula (II):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl, R², R³ and R⁴ independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or substituted orunsubstituted aralkyl. R¹s. R²s, R³s, and R⁴s, when they are eachpresent two or more in number, may be the same or different, R⁹represents a residue derived from a polyisocyanate compound, R¹⁰represents substituted or unsubstituted lower alkylene, substituted orunsubstituted cycloalkylene, or substituted or unsubstituted arylene,and R¹¹, R¹² and R¹³, independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or a substituted orunsubstituted aralkyl), aralkyl.
 6. The urethane acrylate according toclaim 4 or 5, wherein the number-average molecular weight thereof is 200to
 10000. 7. A composition comprising the urethane acrylate according toclaim 4 or 5, and a radical photo-, or thermal polymerization initiator.8. The polyurethane according to claim 1, which is a urethane alkenylether.
 9. An urethane alkenyl ether having a structural unit representedby formula (XI):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl. R², R³ and R⁴ independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or substituted orunsubstituted aralkyl R¹s, R²s, R³s, and R⁴s, when they are each presenttwo or more in number, may be the same or different, R³³ represents aresidue derived from a polyisocyanate compound, R³⁴ represents asubstituted or unsubstituted lower alkylene, substituted orunsubstituted cycloalkylene, or substituted or unsubstituted arylene,and R³⁵, R³⁶ and R³⁷, independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl or substituted orunsubstituted aralkyl.
 10. The urethane alkenyl ether according to claim8 or 9, wherein the number-average molecular weight thereof is 200 to10000.
 11. A composition comprising the urethane alkenyl ether accordingto claim 8 or 9, and a polymerization initiator generating an acidthrough heating or light irradiation.
 12. A composition comprising theurethane alkenyl ether according claim 8 or 9, and a compound having amaleimido group.
 13. The polyurethane according to claim 1 which is apolyester and having hydroxyl groups at its 2, 3, or 4 ends.
 14. Apolyester having a structural unit represented by formula (III):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl substituted or unsubstituted cycloalkylsubstituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl. R², R³ and R⁴ independently represent a hydrogen atomsubstituted or unsubstituted lower alkyl substituted or unsubstitutedcycloalkyl substituted or unsubstituted aryl or substituted orunsubstituted aralkyl, ‘R¹s R²s, R³s, and R⁴s, when they are eachpresent two or more in number may be the same or different, and R¹⁴represents substituted or unsubstituted lower alkylene, substituted orunsubstituted cycloalkylene, or substituted or unsubstituted arylene.15. The polyester according to claim 13 or 14, wherein theweight-average molecular weight thereof is 30000 to
 1000000. 16. Thepolyurethane according to claim 1 which is an ester acrylate havinghydroxyl groups at its 2, 3, or 4 ends.
 17. An ester acrylate having astructural unit represented by formula (IV):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl or substituted or unsubstitutedaralkyl, R², R³ and R⁴ independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl substituted or unsubstituted aryl or substituted orunsubstituted aralkyl, R¹s. R²s, R³s, and R⁴s, when they are eachpresent two or more in number, may be the same or different, and R¹⁵,R¹⁶, and R¹⁷, independently represent a hydrogen atom, substituted orunsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl.
 18. The ester acrylate according to claim 16 or 17, wherein thenumber-average molecular weight thereof is 200 to
 10000. 19. Acomposition comprising the ester acrylate according to claim 16 or 17,and a radical photo-, or thermal polymerization initiator.
 20. Thepolyurethane according to claim 1 which is an alkenyl ether.
 21. Analkenyl ether having a structural unit represented by formula (V):

wherein n represents an integer of 2 to 1000, R¹ represents substitutedor unsubstituted lower alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or substituted or unsubstitutedaralkyl, R², R³ and R⁴ independently represent a hydrogen atom,substituted or unsubstituted lower alkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted aryl, or substituted orunsubstituted aralkyl, R¹s, R²s, R³s, and R⁴s, when they are eachpresent two or more in number, may be the same or different, and R¹⁸,R¹⁹, and R²⁰, which are the same or different, each independentlyrepresent a hydrogen atom, substituted or unsubstituted lower alkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedaryl, or substituted or unsubstituted aralkyl.
 22. The alkenyl etheraccording to claim 20 or 21, wherein the number-average molecular weightthereof is 200 to
 10000. 23. A composition comprising the alkenyl etheraccording to claim 20 or 21 and a polymerization initiator generating anacid through heating or light irradiation.
 24. A composition comprisingthe alkenyl ether according to claim 20 or 21 and a compound having amaleimido group.
 25. A composition comprising the urethane acrylateaccording to claim 6, and a radical photo-, or thermal polymerizationinitiator.
 26. A composition comprising the urethane alkenyl etheraccording to claim 10, and a polymerization initiator generating an acidthrough heating or light irradiation.
 27. A composition comprising theurethane alkenyl ether according to claim 10, and a compound having amaleimido group.
 28. A composition comprising the ester acrylateaccording to claim 18, and a radical photo-, or thermal polymerizationinitiator.
 29. A composition comprising the alkenyl ether according toclaim 22 and a polymerization initiator generating an acid throughheating or light irradiation.
 30. A composition comprising the alkenylether according to claim 22 and a compound having a maleimido group.